A quasi-solid zinc-air battery material interface state layering detection method

Abstract

A quasi-solid-state zinc-air battery material interface state layered detection method belongs to the field of new energy battery state detection, including one open circuit voltage time test of quasi-solid-state zinc-air battery, extracting first-level judgment characteristics; two first-level direct judgment is carried out according to the first-level judgment characteristics, if the layered judgment condition is met, the corresponding result is output, otherwise the OCPT characteristic label is output; three linear sweep voltammetry test is carried out on the battery outputting the OCPT characteristic label, and the output capacity characteristics are extracted; four secondary shunt judgment is carried out according to the output capacity characteristics; five alternating current impedance test is carried out on the output unstable type, output limited type and high output type judgment, and the impedance frequency response characteristics are extracted; six output abnormal type sample joint judgment is carried out on the output limited type and output unstable type, and the abnormal source is confirmed; seven high output type sample joint judgment is carried out on the high output type; eight output diagnosis conclusion is output. The present application realizes the layered judgment of the health state and failure type of the battery material interface.

Description

Technical Field

[0001] This invention relates to the field of state testing technology for new energy batteries and new materials, specifically to a method for detecting the layering of interface state in quasi-solid-state zinc-air battery materials. Background Technology

[0002] Zinc-air batteries, as a new energy battery system that uses oxygen from the air as the positive electrode reactant and metallic zinc as the negative electrode active material, possess advantages such as high theoretical energy density, abundant zinc resources, good safety, and environmental friendliness. They have application potential in fields such as novel energy storage, flexible energy supply, and low-cost backup power. To overcome the problems of leakage, encapsulation difficulties, and safety risks associated with alkaline electrolytes in traditional liquid electrolyte zinc-air batteries, constructing quasi-solid-state zinc-air batteries using polymer gel electrolytes has become one of the important directions in new energy battery material research.

[0003] Quasi-solid-state zinc-air batteries consist of a zinc anode, a gel electrolyte, and an air electrode. Their electrochemical performance depends not only on the individual electrode materials themselves but also heavily on the synergistic effects of the zinc anode / gel electrolyte interface, the gel electrolyte / air electrode interface, and the air electrode catalytic layer. For example, in PANa-based gel electrolyte systems, the gel's hydration state, ion migration channels, and interfacial wetting state directly affect the OH- ion content. - Transmission; In the Co3O4-carbon cloth air electrode system, the integrity of the catalyst layer and the activity of oxygen reduction reaction affect the polarization output capability of the battery; On the zinc negative electrode side, zinc sheet oxidation, corrosion, salting out or passivation will destroy the normal negative electrode reaction interface, resulting in open circuit voltage decay or output capability reduction.

[0004] However, the failure of quasi-solid-state zinc-air batteries does not always manifest as a single, obvious voltage drop. Under certain abnormal material interface conditions, the battery may still maintain a high open-circuit voltage, but exhibit significant anomalies in polarization output or impedance frequency response. For example, when the gel loses water or the effective reaction area of ​​the zinc sheet is limited, the open-circuit voltage may still be close to normal, but the output current at the same polarization amplitude will decrease; when the air electrode catalyst layer is missing, the battery may still have a certain open-circuit voltage, but it can hardly provide effective output in linear sweep voltammetry; when there is slight mass transfer obstruction on the air side, the short-term open-circuit voltage and polarization output may not change significantly, requiring auxiliary judgment based on Bode phase or low-frequency impedance response.

[0005] Existing methods for detecting battery status mostly rely on open-circuit voltage, discharge curves, or single AC impedance spectral parameters. For multi-material, multi-interface coupled systems like quasi-solid-state zinc-air batteries, single detection methods have significant limitations: relying solely on open-circuit voltage can easily misjudge "having open-circuit voltage" as "having normal output capability"; relying solely on polarization curves, while reflecting a decrease in output capability, is difficult to distinguish between different sources such as limited gel transport, zinc sheet obstruction, loose contact, or abnormal air electrodes; relying solely on Nyquist semicircle fitting is also unsuitable for the impedance response of non-ideal, multi-interface coupled quasi-solid-state gel systems, because their impedance curves may exhibit low-frequency extension, oblique linear response, or non-ideal arc shape, rather than a standard single semicircle.

[0006] Therefore, in the research, development, assembly, and storage of new energy quasi-solid-state zinc-air batteries, a layered detection method that can be tailored to the specific material interface state is needed. Summary of the Invention

[0007] To address the problem that existing methods for detecting the state of quasi-solid-state zinc-air batteries (QZ-Air) often fail to accurately distinguish between various abnormal states at material interfaces using only open-circuit voltage, polarization curves, or AC impedance spectra, this invention provides a layered detection method for the interface states of QZ-Air batteries. The method aims to: rapidly identify severe failure states with strong characteristics using open-circuit voltage-time curves; determine whether the battery has actual polarization output capability using linear sweep volt-ampere curves, avoiding misjudging "having open-circuit voltage" as "having normal output capability"; and further differentiate between output-limited or high-output boundary states using impedance frequency response characteristics. Without relying on ideal Nyquist semicircle fitting, this method improves the reliability and applicability of QZ-Air battery material interface state identification through multi-parameter combination criteria, providing technical support for QZ-Air battery material interface failure analysis, assembly quality screening, and storage reliability evaluation.

[0008] To achieve the above objectives, the specific solution of the present invention is as follows:

[0009] A method for detecting the delamination of the interface state of quasi-solid-state zinc-air battery materials, wherein the quasi-solid-state zinc-air battery is composed of a zinc anode, a PANa-based gel electrolyte, and a Co3O4-carbon cloth air electrode, the method for detecting the delamination of the interface state of the quasi-solid-state zinc-air battery materials includes the following steps:

[0010] S1. Perform open-circuit voltage-time test on the solid-state zinc-air battery to be tested, obtain the curve of open-circuit voltage changing with time, and extract the primary judgment features from the curve of open-circuit voltage changing with time. The primary judgment features include the initial open-circuit voltage, the stable open-circuit voltage, the voltage drift rate, the voltage fluctuation amplitude, and the open-circuit voltage hold-up ratio. Furthermore, when the curve of open-circuit voltage changing with time has a sudden drop recovery feature, the primary judgment features also include the sudden drop amplitude and the recovery ratio.

[0011] S2, based on the first-level judgment features extracted in step S1, perform a first-level direct judgment on the interface state of the target solid-state zinc-air battery according to the preset layer judgment conditions: if any of the layer judgment conditions are met, output the first-level direct judgment result corresponding to the met layer judgment conditions; if not met, output the OCPT feature label.

[0012] S3, perform a linear scan volt-ampere test on the quasi-solid-state zinc-air battery to be tested with the output OCPT feature tag described in step S2 to obtain the polarization output curve, and extract the output capability feature from the polarization output curve; the output capability feature includes the characteristic current density under the preset polarization amplitude, the relative output ratio, the output slope in the low polarization region, and the integral area of ​​the current density curve in the polarization region.

[0013] S4. Based on the output capability characteristics extracted in step S3, perform a two-stage shunt determination on the solid-state zinc-air battery under test, and output the two-stage shunt determination result. The two-stage shunt determination result is a near-zero output type determination, an unstable output type determination, a limited output type determination, a high output type determination, or a boundary sample type determination. When the determination result is an unstable output type, a limited output type, or a high output type, proceed to step S5; when the determination result is a near-zero output type determination or a boundary sample type determination, end the test; and provide a retest suggestion for the boundary sample type.

[0014] S5. Perform AC impedance testing on the quasi-solid-state zinc-air battery under test whose secondary shunt determination results are output instability, output limitation, and high output, obtain impedance spectrum data, and extract impedance frequency response features from the impedance spectrum data. The impedance frequency response features include frequency impedance features, phase response features, and trajectory scale features.

[0015] S6. For the quasi-solid-state zinc-air battery to be tested that was determined to be output-limited or output-unstable in step S4, a joint determination of the output-abnormal sample is performed based on the first-level determination characteristics described in step S1, the output capability characteristics described in step S3, and the impedance frequency response characteristics described in step S5, in order to confirm the source of the abnormality of the quasi-solid-state zinc-air battery to be tested that was determined to be output-limited or output-unstable in step S4; the source of the abnormality is the placement attenuation state, loose contact or insufficient contact at the electrode gel interface, and other abnormal states of output-limited or output-unstable.

[0016] S7. For the quasi-solid-state zinc-air battery to be tested that is determined to be of high output type in step S4, based on the fact that its output capability characteristics meet the high output type determination conditions, the high output type impedance frequency response is determined according to the impedance frequency response characteristics in step S5, so as to distinguish the normal state, the air-side mass transfer limited risk state, the slightly abnormal state, and other abnormal states of high output type.

[0017] S8. Based on the primary judgment characteristics of step S1, the output capability characteristics of step S3, and the impedance frequency response characteristics of step S5, combined with the primary judgment results of step S2, the secondary shunt judgment results of step S4, and the joint judgment of abnormal output samples or the high output impedance frequency response judgment results of step S6 or step S7, the diagnostic conclusion of the solid-state zinc-air battery to be tested is output.

[0018] Further, the initial open-circuit voltage mentioned in step S1 is defined as: (1),

[0019] In the formula, This is the initial moment of the OCPT test; This is the initial open-circuit voltage; The open-circuit voltage at the initial moment of the OCPT test;

[0020] The stable open-circuit voltage is defined as the average value of the voltages at several sampling points at the end of the test: (2),

[0021] In the formula, Indicates a stable open-circuit voltage; For the last segment of the test Each sampling voltage; The number of sampling points in the final segment; the final segment of the test selects the last 30 seconds or the last few stable sampling points of the OCPT test.

[0022] The voltage drift rate is defined as: (3),

[0023] In the formula, Indicates voltage drift rate; and These are the open-circuit voltages at the start and end of the selected time period, respectively; and These correspond to the respective times;

[0024] The voltage fluctuation amplitude is defined as: (4),

[0025] In the formula, Indicates the voltage fluctuation range; and These represent the maximum and minimum values ​​of the open-circuit voltage within the test interval, respectively.

[0026] For curves exhibiting a sudden drop followed by a recovery, the magnitude of the drop is further defined as: (5),

[0027] In the formula, Indicates the magnitude of the sudden drop; The platform voltage before the sudden drop. This is the lowest voltage after the sudden drop;

[0028] The recovery ratio is defined as: (6),

[0029] In the formula, Indicates the recovery ratio; This is the open-circuit voltage at the end of the OCPT test;

[0030] The open-circuit voltage holding ratio is defined as:

[0031] (7),

[0032] In the formula, Indicates the open-circuit voltage holding ratio; This represents the stable open-circuit voltage of a normal reference sample.

[0033] Furthermore, in step S2, the interface state of the solid-state zinc-air battery to be tested is directly determined according to the preset layer determination conditions as follows:

[0034] When satisfied When the value is less than 0, the first-level direct judgment result is that the entire battery is in an aging and failure state; where... To stabilize the open-circuit voltage;

[0035] When satisfied and and At that time, the first-level direct judgment result is that the zinc negative electrode is in a severe failure state; among which, Voltage drift rate; Initial open-circuit voltage; This represents the stable open-circuit voltage of a normal reference sample; The preset threshold value close to zero potential is used to characterize that the stable open-circuit voltage of the quasi-solid-state zinc-air battery under test has decayed to near zero potential.

[0036] When satisfied and Or simultaneously satisfy The output first-level direct judgment result is either an abnormal state of zinc sheet oxidation or an abnormal state of the zinc negative electrode surface; among which, The magnitude of the sudden drop; To restore the ratio; Open-circuit voltage holding ratio; The preset threshold for the sudden drop amplitude; The preset recovery ratio threshold; The preset open-circuit voltage hold-up ratio threshold is used;

[0037] Otherwise, output the OCPT feature labels.

[0038] Furthermore, the formula for the characteristic current density under the preset polarization amplitude mentioned in step S3 is as follows:

[0039] (8),

[0040] In the formula, Optional Preset polarization amplitude, ; The samples were selected from the low-polarization, medium-polarization, and high-polarization regions of the linear scan voltammetry curve of the solid-state zinc-air battery to be tested, and there was an interval between adjacent sampling points sufficient to distinguish the output characteristics of different polarization stages.

[0041] The formula for the relative output ratio is as follows:

[0042] (9),

[0043] In the formula, For normal reference samples with the same polarization amplitude; Current density at the following levels;

[0044] The formula for the output slope in the low polarization region is as follows:

[0045] (10)

[0046] In the formula, for Current density near 0; the Used to characterize the early output growth capability of the quasi-solid-state zinc-air battery under test in the low polarization region;

[0047] The integral area of ​​the current density curve within the polarization region includes the integral index of the actual polarization range. and common polarization interval integral index ;

[0048] The actual polarization range integral index The formula is as follows:

[0049] (11),

[0050] In the formula, The maximum polarization amplitude that the solid-state zinc-air battery to be tested can actually cover. Used to characterize the overall output capability of the sample within its actual polarization range.

[0051] When the solid-state zinc-air battery to be tested and the normal reference sample are both covered to the same preset polarization amplitude At that time, the common polarization interval integral index The formula is as follows:

[0052] (12)

[0053] In the formula, The preset polarization amplitude can be covered by both the solid-state zinc-air battery to be tested and the normal reference sample; When = 1, 2, 3, , and These correspond to the low-polarization region, the medium-polarization region, and the high-polarization region, respectively. Used to characterize the solid-state zinc-air battery under test in the common polarization region. Overall output capability within the system.

[0054] Furthermore, the near-zero output type determination condition in step S4 is: satisfying the relative output ratio. or characteristic current density The secondary diversion determination result is that the air electrode catalyst layer is missing;

[0055] The output instability determination condition is as follows: when the polarization output curve exhibits fluctuations, steps, abnormal fluctuations, or premature termination of the effective scan interval, the secondary shunt determination result is an output unstable sample; premature termination of the effective scan interval is expressed as follows: or ,in, For preset polarization amplitude, To preset high polarization amplitude;

[0056] The output-limited determination condition is: if one of the following conditions is met, the secondary shunt determination result is an output-limited sample:

[0057] ,and ,

[0058] ,and ,

[0059] ,and ,

[0060] ,and ,

[0061] ,and ,

[0062] ,and ;

[0063] in, Used to characterize the early output growth capability of the quasi-solid-state zinc-air battery under test in the low polarization region; Used to characterize the solid-state zinc-air battery under test in the common polarization region. Overall output capability within the system; This represents the integral index of a normal reference sample within the same common polarization range. , , These are the relative output ratio thresholds for the low, medium, and high polarization regions used for output-restricted type determination; The output slope threshold is set for the low polarization region; To maintain a threshold for the integral index in the common polarization region;

[0064] The high-output type determination criterion is: when the quasi-solid-state zinc-air battery under test does not meet the near-zero output type, output unstable type, and output limited type determination criteria, it meets the following conditions. or The secondary diversion determination result is a high-output sample; The threshold for high output relative output ratio;

[0065] The criteria for determining the boundary sample type are as follows: samples with unstable output capability characteristics, contradictory criteria for different polarization intervals, insufficient curve coverage, or features near the threshold are marked as boundary sample types, and retesting is recommended.

[0066] Furthermore, the frequency impedance characteristics described in step S5 include low-frequency impedance characteristics, mid-frequency impedance characteristics, high-frequency impedance characteristics, and low-frequency impedance increments;

[0067] The low-frequency impedance characteristics, mid-frequency impedance characteristics, high-frequency impedance characteristics, and low-frequency impedance increment are all calculated using the following formula:

[0068] (13)

[0069] (14)

[0070] (15)

[0071] (16)

[0072] In the formula, Indicates the impedance magnitude; This indicates the low-frequency impedance characteristics, expressed in Ω. The preset low-frequency point is in Hz, preferably around 1Hz; This indicates the mid-frequency impedance characteristic, with the unit being Ω; The preset intermediate frequency point is in Hz, preferably around 100Hz; This indicates the high-frequency impedance characteristics, expressed in Ω. The preset high-frequency point is in Hz, preferably around 10kHz or higher. Indicates the low-frequency impedance increment; This represents the low-frequency impedance of a normal reference sample.

[0073] when When the test is conducted, it is determined that the solid-state zinc-air battery under test has abnormal ion transport, interface polarization, diffusion restriction, or contact state.

[0074] The phase response characteristics include the maximum phase angle and the frequency corresponding to the maximum phase angle; the formula for calculating the maximum phase angle is as follows:

[0075] (17)

[0076] The formula for calculating the frequency corresponding to the maximum phase angle is as follows:

[0077] (18)

[0078] In the formula, The phase angle at frequency f; Indicates the maximum phase angle; This indicates the frequency corresponding to the maximum phase angle; and Used to characterize the hysteresis of the current response relative to voltage disturbances;

[0079] The formula for calculating the trajectory scale features is as follows:

[0080] (19)

[0081] In the formula, This is the low-frequency impedance point; This is the impedance point at the high-frequency end; This indicates the trajectory-scale characteristics, specifically for the air electrode catalyst layer deficiency state. It increases significantly, serving as a characteristic of impedance complex.

[0082] Furthermore, the condition for determining the placement attenuation state in step S6 is: satisfying... and ;in, Open-circuit voltage holding ratio; The preset open-circuit voltage threshold; This represents the low-frequency impedance increment. The preset impedance increment threshold;

[0083] The criteria for determining the state of loose contact or insufficient contact at the electrode-gel interface are as follows: the sample to be tested is determined to be of unstable output type in step S4, and its LSV curve shows obvious fluctuations, steps, local abnormal fluctuations, or premature termination of the effective scan interval, and meets the following conditions. or ;in, Indicates trajectory scale characteristics; Trajectory scale characteristics of normal reference samples;

[0084] The criteria and handling methods for determining other abnormal states of output-limited or output-unstable are as follows: If the sample under test has been determined to be output-limited or output-unstable, but its primary determination characteristics, output capability characteristics, and impedance frequency response characteristics cannot be clearly classified into the placement attenuation state, loose contact, or insufficient contact at the electrode gel interface, it is determined to be other abnormal states of output-limited or output-unstable, and a retest suggestion is given.

[0085] Furthermore, the condition for determining the normal state in step S7 is that the following conditions are met simultaneously:

[0086] ,

[0087] ,

[0088] ,

[0089] in, This represents the low-frequency impedance increment. The preset impedance increment threshold; The maximum phase angle; This represents the maximum phase angle of a normal reference sample. The preset phase angle offset threshold; The frequency corresponding to the maximum phase angle; The frequency corresponding to the maximum phase angle of the normal reference sample; The preset frequency offset threshold;

[0090] The criteria for determining the air-side mass transfer limitation risk state are: the solid-state zinc-air battery under test maintains high output capability in the linear scan voltammetry test in step S3, and the phase response characteristics described in step S5 show a significant shift relative to the normal reference sample.

[0091] The ability to maintain high output must meet one of the following conditions: ,or ;

[0092] The phase response characteristic shows a significant shift relative to the normal reference sample, satisfying the following:

[0093] ;

[0094] When any of the above conditions for maintaining high output capability and the condition for significant shift in maximum phase angle are met simultaneously, the solid-state zinc-air battery to be tested is determined to be in a state of air-side mass transfer limitation risk.

[0095] The criteria for determining the slight abnormal state are as follows: the quasi-solid-state zinc-air battery under test meets the high-output type determination result in step S4, and the impedance frequency response characteristics in step S5 only meet one of the following: low-frequency impedance rise, slight phase peak shift, or slight extension of Nyquist trajectory, and does not reach the determination threshold of the air-side mass transfer limited risk state; when the above conditions are met, a slight abnormality prompt is output and tracking is recommended.

[0096] The criteria for determining other abnormal states of high-output type are as follows: when the quasi-solid-state zinc-air battery to be tested has been determined to be a high-output type sample, but its impedance frequency response characteristics do not meet the criteria for normal state determination, nor do they meet the criteria for air-side mass transfer limited risk state or slight abnormal state determination, or there are inconsistencies between different impedance frequency response characteristics, a high-output type other abnormality prompt will be output, and a retest suggestion will be given.

[0097] Furthermore, the diagnostic conclusion in step S8 includes the status category, main criteria, auxiliary criteria, or retesting recommendations;

[0098] The state categories include normal state, full cell aging state, zinc anode corrosion / salting out / passivation failure state, abnormal zinc sheet oxidation or abnormal zinc anode surface state, missing or significantly failed air electrode catalyst layer state, placement decay state, loose contact or insufficient electrode-gel interface contact state, air obstruction or air-side mass transfer limitation risk state, output-limited or output-unstable other abnormal states, slight abnormal state, and high-output other abnormal states; boundary sample type output retesting suggestion is not considered as a specific material interface state category.

[0099] The main criteria include at least one of the first-level determination features described in step S1, the output capability features described in step S3, and the impedance frequency response features described in step S5.

[0100] Advantages of the present invention

[0101] 1. This invention addresses quasi-solid-state zinc-air batteries composed of a zinc anode, a PANa-based gel electrolyte, and a Co3O4-carbon cloth air electrode. It establishes a layered detection process consisting of a first-level open-circuit voltage identification, a second-level polarization output shunt, and a third-level fine-grained determination of AC impedance. Based on the open-circuit voltage time response, linear scanning volt-ampere polarization output response, and impedance frequency response, this method extracts features such as stable open-circuit voltage, voltage drift rate, polarization output current density, relative output retention rate, low-frequency impedance increment, Bode phase response, and Nyquist trajectory scale. This enables the identification of abnormal material interface states that occur during battery use, storage, or assembly, including zinc anode corrosion / passivation, zinc sheet oxidation, overall battery aging, missing air electrode catalyst layer, impaired air-side mass transfer, and insufficient electrode-gel interface contact.

[0102] 2. This invention utilizes OCPT features to rapidly identify strong characteristic states such as full-cell aging, zinc anode corrosion / salting out / passivation failure, and abnormal zinc sheet oxidation, improving detection efficiency. By analyzing LSV relative polarization amplitude, current density, relative output ratio, and overall output indicators, it can determine whether the battery under test possesses actual polarization output capability, particularly identifying air electrode catalyst layer deficiency states that have open-circuit voltage but lack effective polarization output capability. Through impedance frequency response features such as low-frequency impedance increment, Bode phase response, and Nyquist trajectory scale, it can confirm and subdivide boundary states such as transmission limitation, loose contact, placement attenuation, and air-side mass transfer limitation risks based on LSV shunt results. This method does not rely on ideal Nyquist semicircle fitting and is more suitable for non-ideal, multi-interface coupled quasi-solid-state zinc-air battery systems composed of PANa-based gel electrolytes and Co3O4-carbon cloth air electrodes, providing clearer judgment criteria for battery assembly quality screening, material interface failure analysis, and storage reliability evaluation. Attached Figure Description

[0103] Figure 1 This is a flowchart of a method for detecting the layering of interface states in quasi-solid-state zinc-air battery materials according to the present invention.

[0104] Figure 2 for Figure 1 The flowchart for the first-level direct determination.

[0105] Figure 3 for Figure 1 The flowchart for the secondary diversion determination in the process.

[0106] Figure 4 for Figure 1 The flowchart for the joint determination of abnormal output samples.

[0107] Figure 5 for Figure 1 The flowchart for determining the frequency response of high output impedance.

[0108] Figure 6 This is a schematic diagram of a normal quasi-solid-state zinc-air battery.

[0109] Figure 7 This is a picture of a typical quasi-solid-state zinc-air battery assembly.

[0110] Figure 8 The open-circuit voltage-time curves of the normal reference group, the overall aging group, the zinc sheet corrosion group, the zinc sheet oxidation group, and the zinc sheet oxidation-2 group are provided for embodiments of the present invention.

[0111] Figure 9 for Figure 8 The enlarged view shows the open-circuit voltage curves of the gel dehydration group, the zinc sheet shielding group, the air-blocked group, and the normal reference group.

[0112] Figure 10 Polarization output curves for the normal reference group, gel dehydration group, zinc sheet shielding group, loose contact group, air obstruction group, zinc sheet corrosion group, and zinc sheet oxidation group provided for embodiments of the present invention.

[0113] Figure 11 A comparison chart of polarization output curves of the normal reference group and the bare carbon cloth group provided in an embodiment of the present invention.

[0114] Figure 12 This is a comparison chart of the Nyquist curves for each experimental group except the bare carbon cloth group in this embodiment.

[0115] Figure 13 This is a comparison chart of the Nyquist curves of the normal reference group and the bare carbon cloth group in this embodiment.

[0116] Figure 14The diagram shows the Bode impedance modulus values ​​for the normal group, loose contact group, gel dehydration group, zinc sheet shielding group, bare carbon cloth group, placement attenuation group, zinc sheet oxidation group, zinc sheet corrosion group, and air-obstructed group in this embodiment.

[0117] Figure 15 The Bode phase diagrams for the normal group, loose contact group, gel dehydration group, zinc sheet shielding group, bare carbon cloth group, placement attenuation group, zinc sheet oxidation group, zinc sheet corrosion group, and air-obstructed group in this embodiment are shown. Detailed Implementation

[0118] The present invention will be further explained and described below with reference to the accompanying drawings and specific embodiments. It should be noted that the specific embodiments are not intended to limit the scope of the present invention.

[0119] like Figures 1 to 15 As shown in this specific embodiment, a method for detecting the delamination of the material interface state in a quasi-solid-state zinc-air battery is provided. The quasi-solid-state zinc-air battery is either normally assembled or has a risk of material interface abnormalities. The quasi-solid-state zinc-air battery includes a zinc anode, a PANa-based gel electrolyte, and a Co3O4-carbon cloth air electrode. The method for detecting the delamination of the material interface state in the quasi-solid-state zinc-air battery includes the following steps:

[0120] S1, perform open-circuit voltage-time test and extract first-level judgment features.

[0121] The quasi-solid-state zinc-air battery to be tested is connected to the electrochemical testing equipment and allowed to stand for a preset time. The zinc negative electrode and air electrode are then connected to the test terminals. In this embodiment, the electrochemical testing equipment is a CHI1660F electrochemical workstation manufactured by Shanghai Chenhua Instrument Co., Ltd., used for open-circuit voltage-time testing, linear sweep voltammetry testing, and AC impedance testing. Before testing, the quasi-solid-state zinc-air battery to be tested is allowed to stand for a preset time to ensure that the interfaces between the zinc negative electrode and the gel electrolyte, and between the gel electrolyte and the air electrode, are in a relatively stable contact state. The abnormal risks include, but are not limited to, zinc sheet corrosion, zinc sheet oxidation, gel electrolyte dehydration, missing catalyst layer on the air electrode, air-side obstruction, limited effective reaction area of ​​the zinc sheet, insufficient contact between the electrode and the gel, and performance degradation after storage.

[0122] By allowing the device to settle before testing, the impact of transient contact disturbances on open-circuit voltage, polarization output, and impedance response can be reduced, thereby improving the comparability of subsequent feature extraction.

[0123] The open-circuit voltage-time (OCPT) curve of the quasi-solid-state zinc-air battery under test was obtained by performing an open-circuit voltage-time test. (1),

[0124] In the formula, This represents the open-circuit voltage at test time t. A primary judgment feature is extracted from the curve of open-circuit voltage changing over time. This primary judgment feature includes the initial open-circuit voltage. Stable open-circuit voltage Voltage drift rate Voltage fluctuation amplitude and open-circuit voltage holding ratio Furthermore, when the curve of open-circuit voltage changing over time exhibits a sudden drop-recovery characteristic, the primary criterion also includes the magnitude of the sudden drop. and recovery ratio ;

[0125] The initial open-circuit voltage is defined as:

[0126] (2),

[0127] In the formula, This is the initial moment of the OCPT test; This is the initial open-circuit voltage; The open-circuit voltage at the initial moment of the OCPT test;

[0128] The stable open-circuit voltage Defined as the average voltage of several sampling points at the end of the test:

[0129] (3),

[0130] In the formula, Indicates a stable open-circuit voltage; For the last segment of the test Each sampling voltage; The number of sampling points in the final segment; the final segment of the test selects the last 30 seconds or the last few stable sampling points of the OCPT test.

[0131] The voltage drift rate is defined as:

[0132] (4),

[0133] In the formula, Indicates voltage drift rate; and These are the open-circuit voltages at the start and end of the selected time period, respectively; and These correspond to the respective times;

[0134] The voltage fluctuation amplitude is defined as:

[0135] (5),

[0136] In the formula, Indicates the voltage fluctuation range; and These represent the maximum and minimum values ​​of the open-circuit voltage within the test interval, respectively.

[0137] For curves exhibiting a sudden drop followed by a recovery, the magnitude of the drop is further defined as:

[0138] (6),

[0139] In the formula, Indicates the magnitude of the sudden drop; The platform voltage before the sudden drop. This is the lowest voltage after the sudden drop;

[0140] The recovery ratio is defined as:

[0141] (7),

[0142] In the formula, Indicates the recovery ratio; The open-circuit voltage at the end of the OCPT test; the recovery ratio is used to describe whether partial recovery occurs after a voltage drop.

[0143] Stable open-circuit voltage of normal reference sample For reference, the open-circuit voltage holding ratio is defined as:

[0144] (8),

[0145] In the formula, Indicates the open-circuit voltage holding ratio; Indicates a stable open-circuit voltage; This represents the stable open-circuit voltage of a normal reference sample.

[0146] pass The open-circuit voltage levels of different batches of samples are converted into relative holding capabilities to reduce the impact of absolute voltage fluctuations on the judgment results.

[0147] S2, Perform first-level direct determination based on first-level determination features.

[0148] like Figure 2 As shown, based on the primary judgment features extracted in step S1, a primary direct judgment is performed on states with typical strong features. The interface state of the quasi-solid-state zinc-air battery to be tested, as described in step S1, is directly judged according to preset hierarchical judgment conditions: if any of the hierarchical judgment conditions are met, the primary direct judgment result corresponding to the met hierarchical judgment condition is output; the specific steps for performing the primary direct judgment on the interface state of the quasi-solid-state zinc-air battery to be tested according to the preset hierarchical judgment conditions are as follows:

[0149] When the stable open-circuit voltage is satisfied When the open-circuit voltage is less than 0 and remains in the negative potential range throughout the test period without any tendency to recover to a positive potential, the first-level direct judgment result is that the entire battery is in an aging and failure state. This state indicates that the internal electrochemical balance of the battery has been severely disrupted, and it can be directly identified by the open-circuit voltage time test (OCPT). Subsequent linear sweep voltammetry (LSV) or electrochemical impedance spectroscopy (EIS) tests are not considered necessary steps.

[0150] When satisfied and and When this occurs, the first-level direct judgment result is a severe failure state of the zinc anode; this severe failure state is characterized by the open-circuit voltage continuously decaying from a low potential to near zero potential or in the negative potential range. The severe failure state of the zinc anode includes the destruction of the anode reaction interface caused by zinc sheet corrosion, salting out, passivation, or a combination thereof. Voltage drift rate; Initial open-circuit voltage; This represents the stable open-circuit voltage of a normal reference sample; The preset threshold value is used to characterize that the stable open-circuit voltage of the quasi-solid-state zinc-air battery under test has decayed to near zero potential.

[0151] When satisfied and or simultaneously satisfy The output first-level direct judgment result is either an abnormal state of zinc sheet oxidation or an abnormal state of the zinc negative electrode surface; among which, The magnitude of the sudden drop; To restore the ratio; Open-circuit voltage holding ratio; The preset threshold for the sudden drop amplitude; The preset recovery ratio threshold; The preset open-circuit voltage hold-up ratio threshold.

[0152] in This criterion indicates that although the battery under test shows a recovery trend from a low voltage state, its stable open-circuit voltage retention ratio is still lower than the normal reference level. The abnormal zinc sheet oxidation state or zinc negative electrode surface abnormality is identified by strong OCPT features, and if necessary, further confirmation can be made by combining the low-frequency impedance or phase response in the EIS / Bode features.

[0153] If any sample fails to meet the above-mentioned first-level direct judgment conditions, an OCPT feature tag is output, and the sample proceeds uniformly to the LSV polarization output capability judgment. The OCPT feature tags include tags for near-normal high open-circuit voltage (OCV), medium-low voltage plateau, plateau fluctuation, or low-voltage recovery. This processing method avoids misjudging boundary states such as normal groups, limited gel transport, limited effective zinc sheet area, and air obstruction due to similar open-circuit voltages. The OCPT feature tags indicate that the quasi-solid-state zinc-air battery under test has not triggered the first-level direct judgment and serve as a transitional marker for entering step S3 for output capability feature extraction.

[0154] S3, perform LSV polarization output testing and extract output capability features.

[0155] A linear scan volt-ampere test is performed on the quasi-solid-state zinc-air battery under test that outputs the OCPT feature tag as described in step S2. The quasi-solid-state zinc-air battery under test that outputs the OCPT feature tag refers to the quasi-solid-state zinc-air battery under test that does not directly output a state during the OCPT stage. The polarization output curve (hereinafter referred to as LSV curve) of the current changing with the scan voltage is obtained, and the output capability characteristics are extracted from the polarization output curve. The details are as follows:

[0156] Since the open-circuit voltage of samples in different states may differ, directly comparing LSV curves using absolute voltage as the abscissa would result in inconsistent actual polarization amplitudes experienced by different samples. To improve the comparability between different samples, this embodiment defines relative polarization amplitude:

[0157] (9),

[0158] In the formula, The final stable open-circuit voltage of the solid-state zinc-air battery to be tested; This refers to the instantaneous voltage during the LSV scanning process; This indicates the polarization amplitude relative to the open-circuit voltage.

[0159] Further define current density :

[0160] (10)

[0161] In the formula, is the LSV test current; A is the effective air electrode area.

[0162] The output capability characteristics include the characteristic current density at a preset polarization amplitude. Relative output ratio Low polarization region output slope The integral area of ​​the current density curve within the polarization region .

[0163] The characteristic current density under the preset polarization amplitude The calculation formula is as follows:

[0164] (11),

[0165] In the formula, Indicates current density; Indicated as Preset polarization amplitude, ; The samples were selected from the low-polarization, medium-polarization, and high-polarization regions of the linear scan voltammetry curve of the solid-state zinc-air battery to be tested, and there was an interval between adjacent sampling points sufficient to distinguish the output characteristics of different polarization stages. This indicates the polarization amplitude relative to the open-circuit voltage.

[0166] Preferably, the interval between adjacent sampling points is not less than 0.1V, or not less than the maximum polarization amplitude. 10% of that, correspondingly, will yield:

[0167] (12)

[0168] (13)

[0169] (14)

[0170] In the formula, As a general output capability indicator in the low polarization region; when the LSV curve of the solid-state zinc-air battery under test covers the corresponding polarization range, further extraction is performed. and As an indicator of output capability in the medium-to-high polarization region; This is the instantaneous voltage during the LSV scan process.

[0171] If the LSV curve of the solid-state zinc-air battery to be measured does not cover... = or = If the corresponding feature quantity is not forcibly extracted, only the features within the covered interval are used for judgment.

[0172] Define the relative output ratio The formula is as follows:

[0173] (15)

[0174] In the formula, For normal reference samples with the same polarization amplitude, Current density at the following levels; The sample under test is at the corresponding preset polarization amplitude The current density at that point, =1, 2, and 3 correspond to the low polarization region, medium polarization region, and high polarization region, respectively.

[0175] The formula for the output slope in the low polarization region is as follows:

[0176] (16)

[0177] In the formula, for Current density near 0; the Used to characterize the early output growth capability of the quasi-solid-state zinc-air battery under test in the low polarization region;

[0178] The integral area of ​​the current density curve within the polarization region includes the integral index of the actual polarization range. and common polarization interval integral index .

[0179] The actual polarization range integral index The formula is as follows:

[0180] (17)

[0181] In the formula, The maximum polarization amplitude that the solid-state zinc-air battery to be tested can actually cover. Used to characterize the overall output capability of the sample within its actual polarization range.

[0182] When the solid-state zinc-air battery to be tested and the normal reference sample are both covered to the same preset polarization amplitude At that time, the common polarization interval integral index The formula is as follows:

[0183] (18)

[0184] In the formula, The preset polarization amplitude can be covered by both the solid-state zinc-air battery to be tested and the normal reference sample; When = 1, 2, 3, , and These correspond to the low-polarization region, the medium-polarization region, and the high-polarization region, respectively. Used to characterize the solid-state zinc-air battery under test in the common polarization region. Overall output capability within the system; This indicates that normal reference samples are in the same common polarization range. Internal points indicators.

[0185] When comparing the overall output capability of a solid-state zinc-air battery under test with that of a normal reference sample, samples within the same common polarization range should be used. and Comparison; SLSV is used to characterize the overall output capability of a single sample within its practically coverable polarization range.

[0186] S4, Secondary flow splitting determination based on LSV features

[0187] Based on the output capability characteristics extracted in step S3, a two-stage shunt determination (hereinafter referred to as LSV two-stage shunt) is performed on the quasi-solid-state zinc-air battery under test. The two-stage shunt determination result is output, which can be classified as near-zero output type, unstable output type, limited output type, high output type, or boundary sample type. When the determination result is near-zero output type or boundary sample type, the test ends; when the determination result is unstable output type, limited output type, or high output type, proceed to step S5. The purpose of LSV two-stage shunt is to determine whether the quasi-solid-state zinc-air battery under test has actual polarization output capability, and on this basis, classify the quasi-solid-state zinc-air battery under test into near-zero output type, unstable output type, limited output type, high output type, and boundary sample type, providing a basis for subsequent impedance frequency response characteristics, confirmation, and subdivision. Specifically:

[0188] (1) Near-zero output type determination

[0189] The near-zero output type determination condition is: satisfying the relative output ratio. or characteristic current density Furthermore, when the LSV curve approaches zero current response across the covered polarization range, the second-order shunt determination result indicates a missing air electrode catalyst layer; that is, a bare carbon cloth group or a catalyst layer-deficient group. Although this type of quasi-solid-state zinc-air battery sample may have a certain open-circuit voltage, it cannot provide effective output under polarization conditions, therefore it does not need to be shunted as a general output-limited sample.

[0190] When the solid-state zinc-air battery to be tested does not meet the near-zero output condition, but the LSV curve shows fluctuations, steps, abnormal fluctuations, or premature termination of the effective scan interval, the secondary shunt judgment result is an unstable output sample, and it enters the joint judgment of abnormal output samples, that is, the output-limited group confirmation and subdivision process.

[0191] (2) Output instability determination

[0192] The output instability determination condition is: premature termination of the effective scan interval is represented as follows: or ,in, For preset polarization amplitude, The target solid-state zinc-air battery is designed for high polarization amplitude, but it cannot stably cover the medium-to-high polarization region. This battery may correspond to loose contact, insufficient electrode-gel interface contact, or localized unstable conduction. Further confirmation is needed by combining the impedance frequency response characteristics with low-frequency impedance, Nyquist trajectory scale, or phase response.

[0193] (3) Output-restricted determination

[0194] When the solid-state zinc-air battery under test does not meet the near-zero output type and output instability type criteria, its output capabilities in the low, medium, and high polarization regions are further compared. If the relative output ratio of at least one characteristic polarization region is significantly lower than that of the normal reference sample, that is, if one of the following conditions is met:

[0195] ,and ,

[0196] ,and ,

[0197] ,and ,

[0198] ,and ,

[0199] ,and ,

[0200] ,and ;

[0201] in, Used to characterize the early output growth capability of the quasi-solid-state zinc-air battery under test in the low polarization region; Used to characterize the solid-state zinc-air battery under test in the common polarization region. Overall output capability within the system; This represents the integral index of a normal reference sample within the same common polarization range. , , These are the relative output ratio thresholds for the low, medium, and high polarization regions used for output-restricted type determination; The output slope threshold is set for the low polarization region; To maintain a threshold for the integral index of the common polarization interval.

[0202] The secondary shunt determination result of the quasi-solid-state zinc-air battery under test is then determined to be an output-limited sample, and it enters the joint determination of output-abnormal samples, i.e., the output-limited group confirmation and subdivision process. Furthermore, the quasi-solid-state zinc-air battery under test may correspond to zinc sheet obstruction, placement attenuation, or other output-limited states.

[0203] (4) High output type determination

[0204] When the solid-state zinc-air battery under test does not meet the criteria for near-zero output type, output unstable type, and output limited type, but its high polarization region still maintains high output capability, the high output type criterion is: satisfying or The secondary shunt determination result indicates a high-output sample. The quasi-solid-state zinc-air battery under test is then classified as a high-output impedance-frequency response sample, i.e., a high-output group confirmation and subdivision process. This type of quasi-solid-state zinc-air battery sample still exhibits high polarization output capability in the LSV. Further analysis using impedance-frequency response characteristics will distinguish between normal state, air-side mass transfer-limited risk state, or slightly abnormal state. This is a preset high output relative contrast threshold.

[0205] (5) Boundary sample processing

[0206] For samples with unstable output capability characteristics, contradictory criteria for different polarization intervals, insufficient curve coverage, or features near the threshold, they can be marked as boundary samples, and retesting suggestions can be given.

[0207] Through the above-mentioned LSV two-stage current splitting, this embodiment can further distinguish near-zero output failure, output instability anomaly, output limited anomaly, and samples that meet the high output judgment conditions after the first-stage direct judgment, providing a clear branch for subsequent impedance frequency response characteristic confirmation and subdivision.

[0208] Therefore, in the LSV second-order split determination, the main criterion for the bare carbon cloth group is near-zero output; the main criteria for the gel dehydration group and the zinc sheet shielding group are that the relative output ratio of multiple polarization regions is lower than a preset threshold, the output slope of the low polarization region is lower than a preset threshold, and the integral index of the common polarization interval is lower than the corresponding holding threshold. The criteria are a decrease in the relative output ratio of multiple polarization regions and a decrease in the integral of the common interval; the main criteria for the loose contact group are insufficient curve coverage and unstable output; the main criterion for the air-obstructed group is that the relative output ratio of the medium polarization region or the high polarization region reaches the high output relative output ratio threshold. The above-mentioned main LSV criteria determine whether the sample is directly output or enters the joint determination of output abnormal sample or the determination of high output impedance frequency response. Figure 3 As shown.

[0209] S5, perform impedance frequency response characteristic test and extract impedance frequency response characteristics.

[0210] For the quasi-solid-state zinc-air batteries under test whose secondary current shunting results in step S4 are classified as output instability, output limitation, or high output, AC impedance testing is performed to obtain impedance spectrum data, which is then converted into Nyquist plots, Bode impedance plots, and Bode phase plots. It should be noted that the impedance frequency response characteristic test in this step is not an isolated judgment independent of the OCPT and LSV results. Rather, based on the output capability shunting completed in step S4, it confirms the impedance frequency response and subdivides the sources of anomalies for the quasi-solid-state zinc-air battery samples classified as output instability, output limitation, or high output. For samples entering the joint judgment of output anomaly type samples, the impedance frequency response characteristics are mainly used in conjunction with LSV output decrease or output instability characteristics to confirm conditions such as placement attenuation and loose contact. For samples entering the high output type impedance frequency response judgment, the impedance frequency response characteristics are mainly used, based on the high output type judgment in step 4, to identify normal conditions, air-side mass transfer limitation risks, or minor abnormal conditions.

[0211] Because quasi-solid-state zinc-air batteries involve multiple coupled processes such as zinc anode interface reaction, gel electrolyte ion migration, air electrode oxygen reduction reaction, and oxygen diffusion, their Nyquist curves may not necessarily exhibit an ideal single semicircle. Therefore, this embodiment does not use the diameter of the single semicircle as the sole criterion, but instead extracts impedance frequency response features from the impedance spectrum data. These impedance frequency response features include frequency impedance features, phase response features, and trajectory scale features. Specifically:

[0212] From the real part of the impedance and the imaginary part of impedance Calculate the impedance magnitude:

[0213] (19)

[0214] In the formula, Indicates the impedance magnitude;

[0215] The formula for defining the low-frequency impedance characteristic is as follows:

[0216] (20)

[0217] In the formula, This indicates the low-frequency impedance characteristics, expressed in Ω. The preset low-frequency point is in Hz, preferably around 1Hz.

[0218] The formula for defining the mid-frequency impedance characteristic is as follows:

[0219] (twenty one),

[0220] In the formula, This indicates the mid-frequency impedance characteristic, with the unit being Ω; The preset intermediate frequency point is in Hz, preferably around 100Hz.

[0221] The formula for defining the high-frequency impedance characteristic is as follows:

[0222] (twenty two),

[0223] In the formula, This indicates the high-frequency impedance characteristics, expressed in Ω. The preset high-frequency point is in Hz, preferably around 10kHz or higher.

[0224] Low-frequency impedance of a normal reference sample For reference, define the low-frequency impedance increment:

[0225] (twenty three),

[0226] In the formula, Indicates the low-frequency impedance increment; This represents the low-frequency impedance of a normal reference sample; when When the test is conducted, it is determined that the solid-state zinc-air battery under test has abnormalities in ion transport, interface polarization, diffusion restriction, or contact state.

[0227] The phase response characteristics include the maximum phase angle and the frequency corresponding to the maximum phase angle; the formula for calculating the maximum phase angle is as follows:

[0228] (twenty four),

[0229] The formula for calculating the frequency corresponding to the maximum phase angle is as follows:

[0230] (25),

[0231] In the formula, For frequency The phase angle below; Indicates the maximum phase angle; This indicates the frequency corresponding to the maximum phase angle; and Used to characterize the hysteresis of current response relative to voltage disturbances.

[0232] In addition, Nyquist trajectory scale features are defined. The Nyquist trajectory scale feature is used to characterize the extent of impedance trajectory extension in the low-frequency region. The calculation formula for the Nyquist trajectory scale feature is as follows:

[0233] (26)

[0234] In the formula, This is the low-frequency impedance point; This is the impedance point at the high-frequency end; This indicates the trajectory-scale characteristics, specifically for the air electrode catalyst layer deficiency state. It increases significantly, serving as a characteristic of impedance complex.

[0235] S6, EIS / Bode confirmation and subdivision determination for output-limited or output-unstable branches.

[0236] like Figure 4 As shown, for the quasi-solid-state zinc-air battery to be tested that is determined to be output-limited or output-unstable in step S4, i.e., the quasi-solid-state zinc-air battery to be tested that enters the joint judgment of output-abnormal samples in step S4, a joint judgment is made based on the primary judgment characteristics described in step S1, the output capability characteristics described in step S3, and the impedance frequency response characteristics described in step S5. The impedance frequency response characteristic judgment is not an independent classification separate from the primary judgment characteristics and output capability characteristics, but rather, based on the secondary shunt judgment and output capability characteristics, it combines low-frequency impedance, phase response characteristics, and Nyquist trajectory scale characteristics to confirm and subdivide the abnormal sources of output-limited or output-unstable samples. This is to confirm the abnormal sources of the quasi-solid-state zinc-air battery to be tested that was determined to be output-limited or output-unstable in step S4; the abnormal sources are placement attenuation state, loose contact or insufficient contact at the electrode gel interface, and other abnormal states of output-limited or output-unstable; specifically as follows:

[0237] (1) Placement attenuation state

[0238] The condition for determining the placement attenuation state is: when the following conditions are met. and ;in, Open-circuit voltage holding ratio; The preset open-circuit voltage threshold; This represents the low-frequency impedance increment. To preset the impedance increment threshold, the solid-state zinc-air battery under test was determined to be in a storage degradation state. This storage degradation state is characterized by a decrease in open-circuit voltage retention capability, along with an increase in Bode-Z low-frequency impedance, indicating that the storage process may cause degradation in the gel's aqueous state, interfacial contact, or zinc sheet surface state.

[0239] (2) Loose contact or insufficient contact at the electrode-gel interface

[0240] When the solid-state zinc-air battery under test is determined to be output unstable in step S4, and its LSV curve shows obvious fluctuations, steps, local abnormal fluctuations, local unstable output, or premature termination of the effective scan interval, and meets the following conditions... or ;in, Indicates trajectory scale characteristics; The trajectory scale characteristics of a normal reference sample were used to determine whether the solid-state zinc-air battery under test was in a state of loose contact or insufficient electrode-gel interface contact. This determination was primarily based on the unstable characteristics of the LSV output, supplemented by the increase in mid-to-low frequency impedance or the increase in the Nyquist trajectory scale in the impedance frequency response characteristics. This state of loose contact or insufficient electrode-gel interface contact indicates that there may be insufficient effective contact area, local contact instability, or local discontinuity in the conduction path between the electrode and the gel.

[0241] (3) Other abnormalities such as output-limited or output-unstable types

[0242] Other abnormalities of limited or unstable output are defined as those that cannot be clearly categorized into placement attenuation, loose contact, or insufficient electrode-gel interface contact. The output is classified as another abnormal state of limited or unstable output, and retesting suggestions are provided. It is recommended to confirm this by combining physical conditions, repeating tests, or supplementary characterization.

[0243] S7, Impedance Frequency Response Characteristics Confirmation and Subdivision Judgment of High Output Branch

[0244] like Figure 5 As shown, for the quasi-solid-state zinc-air battery under test whose judgment result in step S4 is high output type, that is, the quasi-solid-state zinc-air battery under test that enters the high output type impedance frequency response judgment, the judgment is made according to the impedance frequency response characteristics in step S5 to distinguish between normal state, air-side mass transfer limited risk state, slight abnormal state, and other abnormal states of high output type. The sample that enters the high output impedance frequency response judgment has already shown high polarization output capability in the LSV stage. Therefore, the focus of this judgment step is not to judge whether its output capability has decreased again, but to combine low-frequency impedance characteristics, phase response characteristics, and Nyquist trajectory scale characteristics to judge whether it has air-side mass transfer limited risk or slight interface anomaly that is not easily exposed in short-term LSV. The details are as follows:

[0245] (1) Normal group

[0246] For the quasi-solid-state zinc-air battery under test that enters the high-output branch in step S4, the normal state and the air-side mass transfer-limited risk state are further distinguished based on the impedance frequency response characteristics.

[0247] When both conditions are met:

[0248] ,

[0249] ,

[0250] ,

[0251] in, This represents the low-frequency impedance increment. The preset impedance increment threshold; The maximum phase angle; This represents the maximum phase angle of a normal reference sample. The preset phase angle offset threshold; The frequency corresponding to the maximum phase angle; The frequency corresponding to the maximum phase angle of the normal reference sample; This is the preset frequency offset threshold.

[0252] The tested quasi-solid-state zinc-air battery was determined to be in a normal state. This normal state indicates that the battery has a stable open-circuit voltage, high polarization output capability, and low impedance level.

[0253] (2) Risk status of limited mass transfer on the air side

[0254] The criteria for determining the air-side mass transfer limitation risk state are as follows: the quasi-solid-state zinc-air battery under test maintains high output capability in the linear scan voltammetry test in step S3, and the phase response characteristics described in step S5 show a significant shift relative to the normal reference sample, thus determining that the quasi-solid-state zinc-air battery under test is in an air-side mass transfer limitation risk state.

[0255] The ability to maintain high output must meet one of the following conditions:

[0256] ,or ;

[0257] The phase response characteristics show a significant shift relative to the normal reference sample, satisfying the following condition:

[0258] ;

[0259] When any of the above conditions for maintaining high output capability and the condition for a significant shift in the maximum phase angle are simultaneously met, the quasi-solid-state zinc-air battery under test is determined to be in a state of air-side mass transfer limitation risk. This state indicates that the sample meets the high-output criteria in short-time LSV polarization testing, but the oxygen diffusion channel, air exposure area, or mass transfer process on the air electrode side may have become abnormal. If the quasi-solid-state zinc-air battery structure under test has air-side obstruction, limited air diffusion channels, or insufficient air electrode exposure area, it can be further confirmed as an air-obstructed state.

[0260] (3) Minor abnormal condition

[0261] The criteria for determining a slight abnormal state are as follows: the quasi-solid-state zinc-air battery under test meets the high-output type determination result in step S4, and the impedance frequency response characteristics in step S5 only exhibit one of the following: low-frequency impedance rise, slight phase peak shift, or slight extension of the Nyquist trajectory, and do not reach the determination threshold for the air-side mass transfer limitation risk state. In this case, the output is considered a slight abnormal state. When the above conditions are met, a slight abnormality alert is output, and follow-up is recommended.

[0262] (4) Other abnormal states of high output

[0263] The criteria for determining other abnormal states of high-output type are as follows: when the quasi-solid-state zinc-air battery to be tested has been determined to be a high-output type sample, but its impedance frequency response characteristics do not meet the criteria for normal state determination, nor do they meet the criteria for air-side mass transfer limited risk state or slight abnormal state determination, or there are inconsistencies between different impedance frequency response characteristics, a high-output type other abnormality prompt will be output, and a retest suggestion will be given.

[0264] S8: Output status category, main criteria, and anomaly level

[0265] Based on the primary judgment characteristics of step S1, the output capability characteristics of step S3, and the impedance frequency response characteristics of step S5, combined with the primary judgment results of step S2, the secondary shunt judgment results of step S4, and the detailed judgment results of step S6 or step S7, the diagnostic conclusion of the solid-state zinc-air battery to be tested is output.

[0266] 1. Components of a Diagnostic Conclusion

[0267] The diagnostic conclusions include the status category, main criteria, auxiliary criteria, or treatment recommendations.

[0268] 2. Definitions of main criteria, auxiliary criteria, and treatment recommendations

[0269] The main criteria refer to the core conditions that directly trigger the state output or determine the sample's entry into the corresponding judgment branch in the stratified judgment process. The main criteria include at least one of the first-level judgment characteristics described in step S1, the output capability characteristics described in step S3, and the impedance frequency response characteristics described in step S5. The main criteria may include, but are not limited to: stable open-circuit voltage, voltage drift rate, drop amplitude, recovery ratio, open-circuit voltage hold-up ratio, relative output ratio, low-polarization region output slope, LSV overall output index, low-frequency impedance increment, Bode phase peak value, and Nyquist trajectory scale; in the normal state judgment, it also includes the offset of the frequency corresponding to the maximum phase angle relative to the frequency corresponding to the normal reference sample.

[0270] The auxiliary criteria refer to additional features used to verify the main criteria, distinguish similar sources of anomalies, or improve the reliability of the judgment.

[0271] The processing suggestions are used to provide guidance on subsequent testing or observation methods when the characteristic quantity of the quasi-solid-state zinc-air battery under test is near the threshold, there are inconsistencies between different criteria, the curve coverage range is insufficient, or the diagnostic result is a slightly abnormal state or other abnormal state; the processing suggestions include retest suggestions and follow-up observation suggestions.

[0272] 3. The state categories include normal state, full cell aging state, zinc anode corrosion / salting out / passivation failure state, abnormal zinc sheet oxidation or abnormal zinc anode surface state, missing or significantly failed air electrode catalyst layer state, placement decay state, loose contact or insufficient electrode-gel interface contact state, air obstruction or air-side mass transfer limitation risk state, output-limited or output-unstable other abnormal states, minor abnormal state, state requiring retesting, and high-output other abnormal states. The suggestion for retesting output for boundary sample types is not considered a specific material interface state category.

[0273] 4. Main criteria for each state category

[0274] The main criteria for judging the aging state of the entire battery are The main criterion for severe failure of the zinc anode is that the open-circuit voltage is <0 and remains in the negative potential range. <0、 ≪ and ≤ The main criteria for judging the abnormal oxidation state of zinc sheets are: > and > ,or ≪ , >0、 < The main criterion for the missing state of the air electrode catalyst layer is: , ≈0 or ≈0, and the LSV curve is close to zero overall. For boundary states such as loose contact, placement attenuation, and air obstruction, the main criteria are jointly composed of LSV shunt characteristics and impedance frequency response characteristics, and the auxiliary criteria include Nyquist trajectory scale and Bode phase peak.

[0275] 5. Types of Composition of Judgment Rules and Main Criteria

[0276] The main criteria include at least one of the following: primary direct judgment, secondary shunt judgment, and impedance frequency response judgment confirmation and subdivision criteria.

[0277] The first-level direct determination is mainly used for the direct identification of strong characteristic states such as aging of the whole battery, severe failure of the zinc negative electrode, and abnormal oxidation of zinc sheet.

[0278] The two-stage shunt determination is mainly used to identify near-zero output, unstable output, limited output, and high output states.

[0279] Impedance frequency response determination is mainly used to identify and subdivide the source of anomalies within the corresponding LSV shunt branch.

[0280] Impedance frequency response determination is not used as an isolated final judgment criterion separate from OCPT and LSV results, but rather constitutes a joint judgment result together with OCPT feature labels and LSV output capability features.

[0281] (1) For samples that enter the joint judgment of output abnormality type samples, impedance frequency response characteristics are mainly used to confirm and subdivide output limited type or output unstable type abnormality.

[0282] (2) For samples that enter the high output impedance frequency response judgment, the impedance frequency response characteristics are mainly used to confirm and subdivide the normal state, air-side mass transfer limited risk state or slightly abnormal state in the high output sample.

[0283] 6. The main criteria in different situations

[0284] For a quasi-solid-state zinc-air battery under test whose primary judgment feature or output capability feature already meets the strong feature criterion, the main criterion is the corresponding primary direct judgment or secondary shunt judgment.

[0285] For samples entering the joint judgment of output anomaly type samples, the main criterion is the joint criterion composed of the previous first-level judgment characteristics, output capability characteristics and impedance frequency response characteristics.

[0286] For samples entering the high-output impedance frequency response criterion, the main criterion is the criterion constituted by the impedance frequency response characteristics.

[0287] 7. Output logic for different state types

[0288] For states with strong features, the decision result can be output in advance at the OCPT or LSV stage;

[0289] For boundary states or overlapping feature states, a joint determination is made by combining OCPT feature labels, output capability features, and impedance frequency response features.

[0290] For samples that directly meet the first-level direct judgment or the second-level diversion judgment, output the corresponding state category and its main criterion;

[0291] For samples entering the joint judgment of abnormal output samples or the judgment of high output impedance frequency response, the state category, main criterion and auxiliary criterion are obtained by jointly confirming the output through the first-level judgment characteristics, output capability characteristics and impedance frequency response characteristics.

[0292] For samples with unstable characteristics, conflicting criteria, or that cannot be clearly classified into a specific state, the output will be "Other anomalies" or "Retest recommended".

[0293] The following test uses a quasi-solid-state zinc-air battery consisting of a zinc sheet negative electrode, PANa (sodium polyacrylate) gel electrolyte, and Co3O4-carbon cloth air electrode as the test object, and the above test method is used for testing.

[0294] The quasi-solid-state zinc-air battery under test is composed of a zinc sheet, a PANa-based gel electrolyte layer, and a Co3O4-carbon cloth air electrode sequentially bonded together. The zinc sheet serves as the negative electrode, the Co3O4-carbon cloth air electrode serves as the air electrode, and the PANa gel electrolyte is located between the two, providing an ion transport channel. Before testing, the battery is allowed to stand for a preset time to ensure that the zinc negative electrode / gel electrolyte interface and the gel electrolyte / air electrode interface are in a relatively stable contact state.

[0295] Ten groups were established: normal group, loose contact group, gel dehydration group, zinc sheet shielding group, bare carbon cloth group, air-blocked group, zinc sheet oxidation group, placement attenuation group, overall aging group, and zinc sheet corrosion group. All data for OCPT, LSV, and EIS in each group were measured and used in the aforementioned testing methods. The specific details are as follows:

[0296] 1. Preparation of PANa-based gel electrolyte layer:

[0297] 1 g of sodium hydroxide was dissolved in 3.7 ml of deionized water. After complete dissolution, 1.4 g of acrylamide (AA), 40 mg of methylenebisacrylamide (Bis), and 0.3 ml of deionized water were added, and the mixture was stirred for 20 min until all the solids were dissolved. 10 mg of ammonium persulfate (APS) and 0.02 ml of tetramethylethylenediamine (TEMED) were added, and the mixture was stirred until fully combined. The resulting mixture was quickly poured into a petri dish, sealed, and allowed to stand for 1 h to allow the polymer to crosslink, thus obtaining a PANa electrolyte membrane. The PANa electrolyte membrane was then immersed in 300 ml of a 6 M potassium hydroxide and 0.2 M zinc acetate solution for 24 h. After swelling, a PANa-based gel electrolyte layer was obtained.

[0298] 2. Preparation of Co3O4-carbon cloth air electrode:

[0299] The carbon cloth was cut into 1cm × 2cm rectangular pieces. After washing with an ultrasonic machine in acetone, anhydrous ethanol, and deionized water for 30 minutes each, it was dried in a 60℃ oven for later use. Catalyst slurry preparation: 27mg of nano-cobalt tetroxide and 63mg of carbon black were weighed using an electronic balance and placed in a mixed solvent containing 0.9mL of Nafion perfluorinated resin solution, 7.2mL of deionized water, and 1.8mL of isopropanol. The mixture was ultrasonicated for 30 minutes to completely dissolve the carbon cloth, thus preparing a heterogeneous catalyst ink slurry. The catalyst slurry was evenly coated onto the carbon cloth using a pipette, with a catalyst loading of 0.4mg / cm² on each piece of carbon cloth. 2 The Co3O4 / carbon cloth composite air electrode can be obtained by drying it in a dry environment at 60℃ for 5 hours.

[0300] 3. Negative electrode preparation:

[0301] Cut the zinc sheet into strips of 2cm x 4cm. Polish the side of the strip that will contact the gel electrolyte, clean it with ethanol, and then dry it for later use. For connection, use a 2cm x 2cm strip as the contact surface, cut the appropriate amount of gel, and use tape or clamps to secure the zinc negative electrode (PANa gel electrolyte) and the Co3O4-carbon cloth air electrode together.

[0302] Normal group: Assemble the materials prepared normally above into a battery.

[0303] Loose Contact Group: During installation, the overall contact is loose, and the adhesive tape is not very secure in fixing the positive and negative electrodes and the gel electrolyte.

[0304] Gel dehydration group: The gel was baked in an oven and weighed before and after. The mass decreased from 1.5635g to 1.1452g, and the water loss rate reached 26.75%. It can be regarded as a gel dehydration group sample.

[0305] Zinc sheet shielding group: 1cm×2cm insulating transparent tape was placed at the contact area between the zinc sheet and the gel, so that the actual contact area between the zinc sheet and the gel was only 50% of that of the normal group.

[0306] Bare carbon cloth group: No Co3O4 was loaded onto the carbon cloth.

[0307] Air-obstructed group: Seal the carbon cloth on the air-facing side with insulating tape, covering half of the area.

[0308] Zinc sheet oxidation assembly: The zinc sheet is baked at 80℃ for 2 hours to form an oxide film, and then installed without polishing.

[0309] Placement of the decay group: The prepared normal group batteries were placed unsealed in room temperature air for one day.

[0310] Overall aging group: The prepared normal group batteries were placed in room temperature air for 10 days without being sealed.

[0311] Zinc sheet corrosion group: Corroded zinc sheets that have been left to stand for 10 days are used to install batteries.

[0312] Test method: Using the Shanghai Chenhua CHI1660F electrochemical workstation, the above-mentioned battery was subjected to OCPT, LSV, and EIS measurements, and the data were recorded and plotted.

[0313] In this embodiment, the open-circuit voltage, polarization stability, and failure degree of different samples are different, therefore the original LSV scan voltage is converted to... Then, the maximum relative polarization amplitude actually covered by each group Not entirely consistent. The relatively stable normal group, gel dehydration group, zinc sheet shielding group, bare carbon cloth group, and air-blocked group can cover above 0.6V, therefore, three feature points of 0.3V, 0.5V, and 0.6V are extracted. The loosely contacted group, due to unstable interface contact, only stably covers approximately 0.519V; therefore, only 0.3V and 0.5V features are extracted, and it is included in the joint judgment of output-unstable and output-abnormal samples. The zinc sheet corrosion group and zinc sheet oxidation group already have strong feature direct judgment criteria in the OCPT stage, and the LSV coverage range is relatively short; therefore, LSV is only used as an auxiliary criterion or not as the primary criterion. For samples not covered to the corresponding polarization amplitude, no extrapolation calculation is performed, and they are indicated by "—" in the table.

[0314] (a) Open-circuit voltage time test and first-level direct determination

[0315] First, open-circuit voltage-time tests were performed on each group of quasi-solid-state zinc-air batteries to obtain curves showing the change of open-circuit voltage over time, and primary judgment features were extracted from these curves. These primary judgment features include the initial open-circuit voltage. Stable open-circuit voltage Voltage drift rate Voltage fluctuation amplitude and open circuit voltage retention ratio When the curve of open-circuit voltage changing over time exhibits a sudden drop and recovery characteristic, the primary criterion also includes the magnitude of the sudden drop. and recovery ratio The purpose of this step is to prioritize the identification of samples with strong characteristics and obvious open-circuit voltage anomalies, and to transfer samples with open-circuit voltages close to normal but with unclear sources of anomaly to subsequent output capability testing.

[0316] like Figure 8As shown, the open-circuit voltage-time curves of each group exhibit different voltage holding capabilities and stability. The curve of the normal reference group is generally stable and can be used as a normal reference; the open-circuit voltage of the overall aging group remains in the negative potential range, showing strong failure characteristics; the open-circuit voltage of the zinc sheet corrosion group decays from a low potential to near zero potential or near a negative potential, indicating that the zinc negative electrode reaction interface has undergone significant degradation; the curve of the zinc sheet oxidation group shows a significant drop and recovery characteristic, indicating that abnormal zinc sheet surface conditions directly affect the open-circuit voltage response. The zinc sheet oxidation group exhibits a drop and recovery type of open-circuit voltage anomaly, while the zinc sheet oxidation-2 group exhibits a low-voltage recovery type of open-circuit voltage anomaly. Both are used to illustrate the different manifestations of abnormal zinc sheet oxidation or zinc negative electrode surface conditions in the open-circuit voltage-time test. Figure 9 As shown, the gel dehydration group, zinc sheet shielding group, air obstruction group, and normal reference group are relatively similar in the local open circuit voltage range, indicating that some material interface anomalies do not necessarily show obvious failure characteristics in the open circuit state, and it is difficult to distinguish the source of the anomaly based solely on the open circuit voltage.

[0317] Stabilizing open-circuit voltage using normal reference group Using 1.3940V as a reference, calculate the open-circuit voltage holding ratio for each group. The results are shown in Table 1.

[0318] Table 1. OCPT Parameter Calculation Demonstration

[0319]

[0320] In this embodiment, a threshold value close to zero potential is used. =0.05V, significant drop threshold =0.20V, recovery ratio threshold =0.30, low open-circuit voltage retention ratio threshold =0.70. Substitute the first-level decision features from Table 1 into the first-level direct decision condition in step S2: when the condition is satisfied... When <0, output the aging and failure status of the entire battery; when the condition is met... <0、 << and ≤ When the zinc negative electrode is in a state of corrosion, salting out, or passivation failure, the output will show these conditions. > and > or satisfy << , >0 and < When the zinc sheet oxidation is abnormal or the zinc negative electrode surface is abnormal, the output will be displayed; other samples that do not meet the above-mentioned first-level direct judgment conditions will be output with OCPT feature tags and proceed to step S3.

[0321] Table 2. Results of Level 1 Direct Judgment and Subsequent Fate

[0322]

[0323] Depend on Figure 8 , Figure 9 As shown in Tables 1 and 2, the overall aging group =-0.3943V, which satisfies the condition. Since the value is less than 0, it is directly determined to be an aging and failure state of the entire battery in step S2.

[0324] Zinc sheet corrosion group =0.3079V, significantly lower than the normal baseline group. =1.3940V, and , ,satisfy <0、 << and ≤ The first-level direct judgment condition is therefore determined to be zinc negative electrode corrosion, salting out or passivation failure state.

[0325] Zinc sheet oxidation group =0.6413V>δ1, =0.3504>δ2, satisfying the condition. > and > The sudden drop and recovery criteria were met, therefore it was determined to be an abnormal zinc sheet oxidation or an abnormal state of the zinc negative electrode surface. Zinc sheet oxidation - Group 2 =0.5702V, significantly lower than =1.3940V, and , =0.5756< ,satisfy << , >0 and < The low-voltage recovery type judgment condition can also be used to determine whether the zinc sheet oxidation is abnormal or the zinc negative electrode surface is abnormal.

[0326] The normal reference group, loose contact group, gel dehydration group, zinc sheet shielding group, air obstruction group, bare carbon cloth group, and placement attenuation group all failed to meet the first-level direct judgment condition in step S2. Therefore, instead of directly outputting a diagnostic conclusion after the open-circuit voltage-time test, the OCPT feature tag is output and the process proceeds to step S3. Among them, the gel dehydration group, zinc sheet shielding group, and air obstruction group... The values ​​were 0.9830, 0.9878, and 0.9968, respectively, all close to the normal baseline level. Figure 9 The similarity in the local open-circuit voltage curves indicates that it is difficult to distinguish the source of the anomaly based solely on open-circuit voltage time testing. (Bare carbon cloth assembly) =1.3122V, =0.9413, still has a certain open circuit voltage, but the open circuit voltage cannot prove that the air electrode catalytic layer has an effective catalytic output capability, so it also proceeds to step S3.

[0327] (II) Linear Scan Volt-Ampere Test and Second-Level Shunt Determination

[0328] For samples that do not directly output a diagnostic conclusion in step S2, a linear sweep voltammetry test is performed to obtain a polarization output curve, and output capability characteristics are extracted from the polarization output curve. These output capability characteristics include the characteristic current density at a preset polarization amplitude, the relative output ratio, the output slope in the low polarization region, and the integral area of ​​the current density curve within the polarization region. The purpose of this step is to determine whether the quasi-solid-state zinc-air battery under test has actual polarization output capability and to categorize the samples into near-zero output type, unstable output type, limited output type, or high output type.

[0329] Since different samples have different open-circuit voltages, this embodiment converts the original scan voltage of the linear scan voltammetry test into a relative polarization amplitude. This is to improve the comparability between different samples. In this embodiment, we take... =0.3V, =0.5V, =0.6V, representing the low, medium, and high polarization regions, respectively. The normal reference group, gel dehydration group, zinc sheet shielding group, bare carbon cloth group, and air-impeded group can cover above 0.6V, so three feature points of 0.3V, 0.5V, and 0.6V are extracted. The loose contact group, due to unstable interface contact, only stably covers about 0.519V, so only the 0.3V and 0.5V features are extracted. The zinc sheet corrosion group and zinc sheet oxidation group complete the first-level direct judgment in the open-circuit voltage-time test, and the subsequent linear scan voltammetry test is not used as the main criterion. Among them, the zinc sheet oxidation group can retain one set of linear scan voltammetry test and AC impedance test data as an auxiliary verification test.

[0330] like Figure 10As shown, the polarization output curves of each group exhibit different output capabilities as the relative polarization amplitude increases. The normal reference group shows stable output in the low, medium, and high polarization regions and can be used as a reference for output capability; although the gel dehydration group and zinc sheet shielding group are close to normal in the open-circuit voltage-time test, their overall output capability decreases in the polarization output curves; the loose contact group shows insufficient effective scanning range or incomplete coverage of the medium and high polarization regions; the air-obstructed group still maintains high output capability in the medium and high polarization regions. Figure 11 As shown, the polarization output curves of the normal reference group and the bare carbon cloth group are particularly different. Although the bare carbon cloth group has a certain open-circuit voltage, its polarization output curve is close to zero output, indicating that "having an open-circuit voltage" is not the same as "having normal output capability".

[0331] The output capability characteristics were extracted based on the polarization output curve, and the results are shown in Table 3.

[0332] Table 3. LSV Parameter Calculation Demonstration

[0333]

[0334] Table 4. LSV parameter calculation demonstration (continued)

[0335]

[0336] In this embodiment, a preset polarization amplitude is used. =0.3V, =0.5V, =0.6V, corresponding to the low, medium, and high polarization regions, respectively; the corresponding integral indices for the common polarization region are denoted as... , and The near-zero output relative output ratio threshold is set to 0.05; the relative output ratio thresholds for the low, medium, and high polarization regions used for output-limited type determination are respectively... =0.70、 =0.70、 =0.70, take the output slope threshold in the low polarization region. =8.0, take the common polarization interval integral index to maintain the threshold. =0.70; Alternatively, select a high output relative output ratio threshold. =0.90. When When the relative output ratio of the corresponding polarization region is lower than the preset threshold, it can be determined that the corresponding output-limited condition is met. Substituting the output capability characteristics in Tables 3 and 4 into the secondary shunt determination condition in step S4, the results shown in Table 5 are obtained.

[0337] Table 5. Results of Secondary Diversion and Subsequent Destinations

[0338]

[0339] Depend on Figure 10 , Figure 11 As shown in Tables 3 and 4, the bare carbon cloth group =0.0089、 =0.0104、 =0.0147, all of which are not greater than the near-zero output relative output ratio threshold of 0.05, thus satisfying the near-zero output type determination condition. Furthermore... =0.0311, significantly lower than the normal baseline group. =2.8662, which can serve as further evidence of its near-zero output characteristic. Therefore, this group is determined to be of the near-zero output type in step S4, and outputs a state of missing air electrode catalyst layer.

[0340] Contact loose group =1.3607、 =0.7766, but its curve does not cover the area. =0.6V, meaning the maximum polarization amplitude that can actually be covered. < The output instability condition is met, and the process proceeds to step S5. In step S6, a joint determination is made by combining the first-level determination feature, output capability feature, and impedance frequency response feature.

[0341] Gel dehydration group =0.5629、 =0.4852、 =0.5044, respectively satisfying < , < and < Meanwhile, K 0-0.3 =6.0189< , =1.4867< =0.70×2.8662=2.0063, therefore the output-limited judgment condition is met, proceed to step S5, and in step S6, the joint judgment of output-abnormal samples is performed. Zinc sheet blocking group =0.6049、 =0.5664、 =0.5582, respectively satisfying < , < and < Meanwhile, K 0-0.3 =-2.8150< , =1.6357< Therefore, it is also determined to be an output-limited type. This is consistent with step S2. =0.9878≈1, which further indicates that this group belongs to the samples whose open-circuit voltage is close to normal but whose actual output capability is reduced.

[0342] Air obstruction group =1.0971≥ =0.90、 =1.1005≥ =0.90, which meets the high-output type criterion, therefore proceed to step S5, and further determine based on impedance frequency response characteristics in step S7. Its common polarization interval integral index =3.1923> This indicates that the overall output capability of this group did not decrease within the same polarization range. This result is for supplementary explanation and is not an independent condition for determining high output. Normal baseline group As a normal reference for high output, it also proceeds to steps S5 and S7 to confirm the normal status.

[0343] In this embodiment, no separate boundary sample type test group is set up. If the output capability characteristics of the solid-state zinc-air battery to be tested are near the threshold, the judgment results of different polarization regions are contradictory, or the curve coverage is insufficient and it cannot be stably classified into near-zero output type, unstable output type, limited output type, or high output type, then in step S4, the boundary sample type judgment is output, the detection is ended, and a retest suggestion is output.

[0344] (III) AC impedance testing and impedance frequency response feature extraction

[0345] For samples that proceed to step S5 after the two-stage current shunting determination, AC impedance testing is performed to obtain Nyquist plots, Bode impedance plots, and Bode phase plots, and low-frequency impedance characteristics are extracted. Mid-frequency impedance characteristics High-frequency impedance characteristics Low-frequency impedance increment Maximum phase angle The frequency corresponding to the maximum phase angle and Nyquist trajectory scale The purpose of this step is to: for samples with unstable or limited output, proceed to step S6 for joint determination of abnormal output samples; for samples with high output, proceed to step S7 for determination of high output impedance frequency response.

[0346] like Figure 12As shown, the Nyquist curves in each group do not all exhibit an ideal single semicircle, but rather show low-frequency extension, trajectory scale variation, or non-ideal impedance response characteristics. Therefore, this embodiment does not use the diameter of the single semicircle as the sole criterion, but instead extracts... , and Equal impedance frequency response characteristics. Except for the bare carbon cloth group, the Nyquist curves of most other groups are concentrated in the lower impedance range, but the degree of low-frequency tail extension and trajectory scale still vary.

[0347] like Figure 13 As shown, the impedance response of the bare carbon cloth group differs significantly from that of the normal reference group. (Normal reference group) =12.4947Ω, =12.5786; bare carbon cloth group =1243.9650Ω, which is 99.5596 times that of the normal reference group. / =98.9013. This result indicates that the absence of the air electrode catalyst layer leads to an order-of-magnitude increase in low-frequency impedance and Nyquist trajectory scale, which is consistent with the near-zero output of the bare carbon cloth group in step S4. Therefore, the AC impedance test can be used as an auxiliary verification of the absence state of the air electrode catalyst layer.

[0348] In this embodiment, the low-frequency impedance characteristic is taken as the impedance magnitude at 1Hz, the mid-frequency impedance characteristic is taken as the impedance magnitude at 100Hz, and the high-frequency impedance characteristic is taken as the impedance magnitude at 9985Hz; using the normal reference group as a reference, further calculations are performed. / and / The parameters are used to characterize the low-frequency impedance amplification and the extension of the Nyquist trajectory. The parameters for each group are shown in Tables 6 and 7.

[0349] Table 6. EIS Parameter Calculation Demonstration

[0350]

[0351] Table 7. EIS Parameter Calculation Display (Continued)

[0352]

[0353] like Figure 14 As shown in Tables 6 and 7, each group exhibits different low-frequency impedance responses in the Bode impedance diagram. The low-frequency impedances of the attenuation group, gel dehydration group, and zinc sheet shielding group all increased to varying degrees compared to the normal reference group. Among these, the attenuation group showed the most significant increase. / =2.3869, gel dehydration group / =1.2448, Zinc sheet shielding group / =1.3387. The above-mentioned increase in low-frequency impedance indicates that the solid-state zinc-air battery under test may have abnormal states such as limited ion transport, enhanced interface polarization, reduced effective reaction area, or storage decay. Therefore, for the sample that was shunted into an output-limited type in step S4, the low-frequency impedance increment can be... This serves as an important auxiliary criterion for the joint determination of anomalous samples output in step S6.

[0354] like Figure 15 As shown in Tables 6 and 7, the Bode phase diagrams of each group differ in terms of maximum phase angle. Normal baseline group =57.09°, which can be used as a phase response reference; air-impeded group =64.31°, offset by 7.22° relative to the normal reference group; loose contact group =37.81°, a deviation of 19.28° relative to the normal reference group. The above phase response difference indicates that even if the low-frequency impedance of some samples does not increase significantly, there may still be abnormal air-side mass transfer or interface response. It is necessary to combine the output capability characteristics to jointly determine the abnormal output type of sample or the high output type impedance frequency response.

[0355] (iv) Joint Judgment of Abnormal Output Samples

[0356] In this embodiment, the low-frequency impedance of the normal reference group is used. =12.4947Ω, maximum phase angle =57.09°, trajectory scale =12.5786 is used as a reference; the low-frequency impedance increment threshold is taken. =0.10, phase angle offset threshold =5°. For the quasi-solid-state zinc-air battery under test whose judgment result in step S4 is unstable output or limited output, the abnormal output sample is jointly judged according to the first-level judgment characteristics in step S1, the output capability characteristics in step S3, and the impedance frequency response characteristics in step S5, so as to confirm the abnormal source of the quasi-solid-state zinc-air battery under test.

[0357] Table 8. Joint Judgment Results of Output Abnormal Samples for Output-Limited and Output-Unstable Samples

[0358] As shown in Table 8, the loose contact group satisfies the following in step S4. < The output instability condition was further measured. =0.1275> ,and =19.28°> Therefore, considering the unstable output characteristics and abnormal impedance frequency response, it was determined to be a state of loose contact or insufficient contact at the electrode-gel interface.

[0359] Both the gel dehydration group and the zinc sheet blocking group were determined to be output-limited in step S4. Specifically, the relative output ratios of multiple polarization regions in the gel dehydration group were all below the corresponding thresholds. =1.4867< =2.0063; the relative output ratios of multiple polarization regions in the zinc sheet blocking group are also lower than the corresponding thresholds, and =1.6357< =2.0063, therefore both groups meet the output-limited judgment condition and proceed to step S6. Further verification shows that the gel dehydration group RU=0.9830≈1 and the zinc sheet blocking group RU=0.9878≈1, neither of which meets the judgment condition for placement attenuation state; neither group showed output instability characteristics in step S4, therefore they do not meet the judgment condition for loose contact or insufficient electrode-gel interface contact state. Although the gel dehydration group =0.2448> , / =1.2538, Zinc sheet shielding group =0.3387> / =1.3302 indicates that there are abnormal impedance responses in both groups. According to the joint judgment rule in step S6, both groups were judged to be output-limited in step S4. According to the joint judgment rule in step S6, the output is either output-limited or output-unstable or other abnormal state, and a retest suggestion is given.

[0360] In step S2, the attenuation group is placed. =0.5736< This indicates a significant decrease in the open-circuit voltage holding capability; further measurements... =1.3869> , / =2.3869, / =2.3810, which meets the criteria of decreased open-circuit voltage holding capability accompanied by increased low-frequency impedance, therefore it is determined to be in a placement attenuation state.

[0361] (v) Determination of high output impedance frequency response

[0362] For the quasi-solid-state zinc-air battery under test that was determined to be of high output type in step S4, impedance frequency response is determined based on the impedance frequency response characteristics in step S5 to distinguish between normal state, air-side mass transfer limited risk state, slightly abnormal state, and other abnormal states of high output type. In this embodiment, the normal reference group and the air-impeded group are high output type samples, so the process proceeds to step S7.

[0363] Table 9. Impedance-frequency response determination results for high-output samples.

[0364]

[0365] As shown in Table 9, the normal baseline group =1.0000, =0, and =0≤ , The condition meets the criteria for normal operation. The air-obstructed group meets the criteria for high-output operation in step S4, wherein... =1.0971≥ =0.90, =1.1005≥ =0.90, indicating that its short-time polarization output capability has not decreased significantly; further measurements =64.31°, relative to the normal reference group =57.09° offset by 7.22°, which satisfies > Although this group =-0.0107, the low-frequency impedance did not increase significantly, but it met the S7 judgment condition of "maintaining high output capability and significant phase response shift", so it was judged as a risk state of limited mass transfer on the air side.

[0366] Furthermore, the bare carbon cloth group has already met the near-zero output type determination condition in step S4, and further measurements were performed. / =99.5596, / =98.9013, indicating that its low-frequency impedance and Nyquist trajectory scale are orders of magnitude larger than the normal reference group, which can serve as supplementary evidence of the missing state of the air electrode catalyst layer. The zinc sheet oxidation group and the zinc sheet corrosion group have completed the first-level direct judgment in step S2, and the EIS data is only used as auxiliary verification information and not as the main criterion; the zinc sheet oxidation-2 group is a low-voltage recovery style display group of open circuit voltage time test, and LSV and EIS data will not be repeated in the future.

[0367] (vi) Output of diagnostic conclusions

[0368] Based on the primary judgment characteristics, output capability characteristics, and impedance frequency response characteristics, combined with the primary direct judgment results, the secondary shunt judgment results, and the judgment results of step S6 or step S7, a diagnostic conclusion for the solid-state zinc-air battery under test is output. The diagnostic conclusion includes the state category, primary criterion, and auxiliary criteria, as shown in Table 10.

[0369] Table 10 Output Table of Diagnostic Conclusions for Solid-State Zinc-Air Batteries to be Tested

[0370]

[0371] From Table 1 to Table 10 and Figures 8 to 15 As can be seen, in this embodiment, various types of quasi-solid-state zinc-air batteries under test exhibit different characteristics in open-circuit voltage-time curves, linear sweep volt-ampere curves, Nyquist plots, Bode impedance plots, and Bode phase plots. The overall aging group, zinc sheet corrosion group, and zinc sheet oxidation group already exhibit strong characteristics in their open-circuit voltage-time curves, allowing for direct diagnostic conclusions based on primary diagnostic features. While the bare carbon cloth group possesses a certain open-circuit voltage, its linear sweep voltammetry curve is close to zero output, and it shows a significant increase in low-frequency impedance and trajectory size in the Nyquist and Bode impedance diagrams, thus indicating a missing air electrode catalyst layer. The gel dehydration group and zinc sheet shielding group appear near normal in their open-circuit voltage curves, but their output capability decreases in their linear sweep voltammetry curves, and they exhibit low-frequency impedance or increased trajectory size in their impedance frequency response, thus indicating output-limited abnormalities, and a retest recommendation is given. The loose contact group is confirmed through a combination of unstable output characteristics and abnormal impedance frequency response. The air-obstructed group meets the high-output criteria in its short-time polarization output, but its phase response in the Bode phase diagram shows a significant shift, thus indicating a risk of air-side mass transfer limitation.

[0372] The above results demonstrate that this invention does not rely solely on open-circuit voltage, linear scanning volt-ampere curves, or AC impedance parameters for judgment. Instead, it follows a hierarchical detection logic of "first-level judgment characteristics—output capability characteristics—impedance frequency response characteristics," combining curve morphology, parameter extraction, and hierarchical judgment to progressively screen and confirm the material interface state of the quasi-solid-state zinc-air battery. This method avoids misjudging "having open-circuit voltage" as "having normal output capability" and can further distinguish different abnormal states such as missing air electrode catalyst layer, limited air-side mass transfer, loose contact, placement attenuation, zinc sheet oxidation, zinc sheet corrosion, and overall battery aging.

Claims

1. A method for detecting the delamination of the interface state of quasi-solid-state zinc-air battery materials, characterized in that, The quasi-solid-state zinc-air battery includes a zinc anode, a PANa-based gel electrolyte, and a Co3O4-carbon cloth air electrode. A method for detecting the layering of the material interface states in the quasi-solid-state zinc-air battery includes the following steps: S1. Perform open-circuit voltage-time test on the solid-state zinc-air battery to be tested, obtain the curve of open-circuit voltage changing with time, and extract the primary judgment features from the curve of open-circuit voltage changing with time. The primary judgment features include the initial open-circuit voltage, the stable open-circuit voltage, the voltage drift rate, the voltage fluctuation amplitude, and the open-circuit voltage hold-up ratio. Furthermore, when the curve of open-circuit voltage changing with time has a sudden drop recovery feature, the primary judgment features also include the sudden drop amplitude and the recovery ratio. S2, based on the first-level judgment features extracted in step S1, perform a first-level direct judgment on the interface state of the target solid-state zinc-air battery according to the preset layer judgment conditions: if any of the layer judgment conditions are met, output the first-level direct judgment result corresponding to the met layer judgment conditions; if not met, output the OCPT feature label. S3, perform a linear scan volt-ampere test on the quasi-solid-state zinc-air battery to be tested with the output OCPT feature tag described in step S2 to obtain the polarization output curve, and extract the output capability feature from the polarization output curve; the output capability feature includes the characteristic current density under the preset polarization amplitude, the relative output ratio, the output slope in the low polarization region, and the integral area of ​​the current density curve in the polarization region. S4. Based on the output capability characteristics extracted in step S3, perform a two-stage shunt determination on the solid-state zinc-air battery to be tested, and output the two-stage shunt determination result. The two-stage shunt determination result is a near-zero output type determination, an unstable output type determination, a limited output type determination, a high output type determination, or a boundary sample type determination. When the determination result is an unstable output type, a limited output type, or a high output type, proceed to step S5; when the determination result is a near-zero output type determination or a boundary sample type determination, end the test, and provide a retest suggestion for the boundary sample type. S5. Perform AC impedance testing on the quasi-solid-state zinc-air battery under test whose secondary shunt determination results are output instability, output limitation, and high output, obtain impedance spectrum data, and extract impedance frequency response features from the impedance spectrum data. The impedance frequency response features include frequency impedance features, phase response features, and trajectory scale features. S6. For the quasi-solid-state zinc-air battery to be tested that was determined to be output-limited or output-unstable in step S4, a joint determination of the output-abnormal sample is performed based on the first-level determination characteristics described in step S1, the output capability characteristics described in step S3, and the impedance frequency response characteristics described in step S5, in order to confirm the source of the abnormality of the quasi-solid-state zinc-air battery to be tested that was determined to be output-limited or output-unstable in step S4; the source of the abnormality is the placement attenuation state, loose contact or insufficient contact at the electrode gel interface, and other abnormal states of output-limited or output-unstable. S7. For the quasi-solid-state zinc-air battery to be tested that is determined to be of high output type in step S4, based on the fact that its output capability characteristics meet the high output type determination conditions, the high output type impedance frequency response determination is carried out according to the impedance frequency response characteristics in step S5, so as to distinguish the normal state, the air-side mass transfer limited risk state, the slight abnormal state, and other abnormal states of high output type. S8. Based on the primary judgment characteristics of step S1, the output capability characteristics of step S3, and the impedance frequency response characteristics of step S5, combined with the primary judgment results of step S2, the secondary shunt judgment results of step S4, and the joint judgment of abnormal output samples or the high output impedance frequency response judgment results of step S6 or step S7, the diagnostic conclusion of the solid-state zinc-air battery to be tested is output.

2. The method according to claim 1, characterized in that, The initial open-circuit voltage mentioned in step S1 is defined as follows: （1）， In the formula, This is the initial moment of the OCPT test; This is the initial open-circuit voltage; The open-circuit voltage at the initial moment of the OCPT test; The stable open-circuit voltage is defined as the average value of the voltages at several sampling points at the end of the test: （2）， In the formula, Indicates a stable open-circuit voltage; For the last segment of the test Each sampling voltage; The number of sampling points in the final segment; the final segment of the test selects the last 30 seconds or the last few stable sampling points of the OCPT test. The voltage drift rate is defined as: （3）， In the formula, Indicates voltage drift rate; and These are the open-circuit voltages at the start and end of the selected time period, respectively; and These correspond to the respective times; The voltage fluctuation amplitude is defined as: （4）， In the formula, Indicates the magnitude of voltage fluctuation; and These represent the maximum and minimum values ​​of the open-circuit voltage within the test interval, respectively. For curves exhibiting a sudden drop followed by a recovery, the magnitude of the drop is further defined as: （5）， In the formula, Indicates the magnitude of the sudden drop; The platform voltage before the sudden drop. This is the lowest voltage after the sudden drop; The recovery ratio is defined as: （6）， In the formula, Indicates the recovery ratio; This is the open-circuit voltage at the end of the OCPT test; The open-circuit voltage holding ratio is defined as: （7）， In the formula, Indicates the open-circuit voltage holding ratio; This represents the stable open-circuit voltage of a normal reference sample.

3. The method according to claim 1, characterized in that, Step S2 describes the first-level direct determination of the interface state of the solid-state zinc-air battery to be tested according to the preset layer determination conditions, as follows: When satisfied When the value is less than 0, the first-level direct judgment result is that the entire battery is in an aging and failure state; where... To stabilize the open-circuit voltage; When satisfied and and At that time, the first-level direct judgment result is that the zinc negative electrode is in a severe failure state; among which, Voltage drift rate; Initial open-circuit voltage; This represents the stable open-circuit voltage of a normal reference sample; The preset threshold value close to zero potential is used to characterize that the stable open-circuit voltage of the quasi-solid-state zinc-air battery under test has decayed to near zero potential. When satisfied and Or simultaneously satisfy The output first-level direct judgment result is either an abnormal state of zinc sheet oxidation or an abnormal state of the zinc negative electrode surface; among which, The magnitude of the sudden drop; To restore the ratio; Open-circuit voltage holding ratio; The preset threshold for the sudden drop amplitude; The preset recovery ratio threshold; The preset open-circuit voltage hold-up ratio threshold is used; Otherwise, output the OCPT feature labels.

4. The method according to claim 1, characterized in that, The characteristic current density formula under the preset polarization amplitude mentioned in step S3 is as follows: （8）， In the formula, Optional Preset polarization amplitude, ; The samples were selected from the low-polarization, medium-polarization, and high-polarization regions of the linear scan voltammetry curve of the solid-state zinc-air battery to be tested, and there was an interval between adjacent sampling points sufficient to distinguish the output characteristics of different polarization stages. The formula for the relative output ratio is as follows: （9）， In the formula, This indicates that normal reference samples have the same relative polarization amplitude. Current density at the following levels; The formula for the output slope in the low polarization region is as follows: （10）， In the formula, for Current density near 0; The Used to characterize the early output growth capability of the quasi-solid-state zinc-air battery under test in the low polarization region; The integral area of ​​the current density curve within the polarization region includes the integral index of the actual polarization range. and common polarization interval integral index ; The actual polarization range integral index The formula is as follows: （11）， In the formula, The maximum polarization amplitude that the solid-state zinc-air battery to be tested can actually cover. Used to characterize the overall output capability of the sample within its actual polarization range; When the solid-state zinc-air battery to be tested and the normal reference sample are both covered to the same preset polarization amplitude At that time, the common polarization interval integral index The formula is as follows: （12）， In the formula, The preset polarization amplitude can be covered by both the solid-state zinc-air battery to be tested and the normal reference sample; When = 1, 2, 3, , and These correspond to the low-polarization region, the medium-polarization region, and the high-polarization region, respectively. Used to characterize the solid-state zinc-air battery under test in the common polarization region. Overall output capability within the system.

5. The method according to claim 1, characterized in that, The near-zero output type determination condition mentioned in step S4 is: satisfying the relative output ratio. or characteristic current density The secondary diversion determination result is that the air electrode catalyst layer is missing; The output instability determination condition is as follows: when the polarization output curve exhibits fluctuations, steps, abnormal fluctuations, or premature termination of the effective scan interval, the secondary shunt determination result is an output unstable sample; premature termination of the effective scan interval is expressed as follows: or ,in, For preset polarization amplitude, To preset high polarization amplitude; The output-limited determination condition is: if one of the following conditions is met, the secondary shunt determination result is an output-limited sample: ,and , ,and , ,and , ,and , ,and , ,and ; in, Used to characterize the early output growth capability of the quasi-solid-state zinc-air battery under test in the low polarization region; Used to characterize the solid-state zinc-air battery under test in the common polarization region. Overall output capability within the system; This represents the integral index of a normal reference sample within the same common polarization range. , , These are the relative output ratio thresholds for the low, medium, and high polarization regions used for output-restricted type determination; The output slope threshold is set for the low polarization region; To maintain a threshold for the integral index within the common polarization region; the high-output type determination condition is: when the quasi-solid-state zinc-air battery under test does not meet the near-zero output type, output unstable type, and output limited type determination conditions, it satisfies... or The secondary diversion determination result is a high-output sample; The threshold for high output relative output ratio; The criteria for determining the boundary sample type are as follows: samples with unstable output capability characteristics, contradictory criteria for different polarization intervals, insufficient curve coverage, or features near the threshold are marked as boundary sample types, and retesting is recommended.

6. The method according to claim 1, characterized in that, The frequency impedance characteristics described in step S5 include low-frequency impedance characteristics, mid-frequency impedance characteristics, high-frequency impedance characteristics, and low-frequency impedance increments; The low-frequency impedance characteristics, mid-frequency impedance characteristics, high-frequency impedance characteristics, and low-frequency impedance increment are all calculated using the following formula: （13）， （14）， （15）， （16）， In the formula, Indicates the impedance magnitude; This indicates the low-frequency impedance characteristics, expressed in Ω. The preset low-frequency point is in Hz, preferably around 1Hz; This indicates the mid-frequency impedance characteristic, with the unit being Ω; The preset intermediate frequency point is in Hz, preferably around 100Hz; This indicates the high-frequency impedance characteristics, with units of Ω. The preset high-frequency point is in Hz, preferably around 10kHz or higher. Indicates the low-frequency impedance increment; This represents the low-frequency impedance of a normal reference sample. when When the test is conducted, it is determined that the solid-state zinc-air battery under test has abnormal ion transport, interface polarization, diffusion restriction, or contact state. The phase response characteristics include the maximum phase angle and the frequency corresponding to the maximum phase angle; the formula for calculating the maximum phase angle is as follows: （17）， The formula for calculating the frequency corresponding to the maximum phase angle is as follows: （18）， In the formula, For frequency The phase angle below; Indicates the maximum phase angle; This indicates the frequency corresponding to the maximum phase angle; and Used to characterize the hysteresis of the current response relative to voltage disturbances; The formula for calculating the trajectory scale features is as follows: （19）， In the formula, This is the low-frequency impedance point; This is the impedance point at the high-frequency end; This indicates the trajectory-scale characteristics, specifically for the air electrode catalyst layer deficiency state. It increases significantly, serving as a characteristic of impedance complex.

7. The method according to claim 1, characterized in that, The condition for determining the placement attenuation state in step S6 is: satisfying the following conditions. and ;in, Open-circuit voltage holding ratio; The preset open-circuit voltage threshold; This represents the low-frequency impedance increment. The preset impedance increment threshold; The criteria for determining the state of loose contact or insufficient contact at the electrode gel interface are as follows: the sample to be tested is determined to be of unstable output type in step S4, and its LSV curve shows fluctuations, steps, local abnormal fluctuations, or premature termination of the effective scan interval, and meets the following conditions. or ;in, Indicates trajectory scale characteristics; Trajectory scale characteristics of normal reference samples; The criteria and handling methods for determining other abnormal states of output-limited or output-unstable are as follows: If the sample under test has been determined to be output-limited or output-unstable, but its primary determination characteristics, output capability characteristics, and impedance frequency response characteristics cannot be clearly classified into the placement attenuation state, loose contact, or insufficient contact at the electrode gel interface, it is determined to be other abnormal states of output-limited or output-unstable, and a retest suggestion is given.

8. The method according to claim 1, characterized in that, The condition for determining the normal state in step S7 is that the following conditions are met simultaneously: , ， ， in, This represents the low-frequency impedance increment. The preset impedance increment threshold; The maximum phase angle; This represents the maximum phase angle of a normal reference sample. The preset phase angle offset threshold is used; The frequency corresponding to the maximum phase angle; The frequency corresponding to the maximum phase angle of the normal reference sample; The preset frequency offset threshold; The criteria for determining the air-side mass transfer limitation risk state are: the solid-state zinc-air battery under test maintains high output capability in the linear scan voltammetry test in step S3, and the phase response characteristics described in step S5 show a significant shift relative to the normal reference sample. The ability to maintain high output must meet one of the following conditions: ,or ; The phase response characteristics show a significant shift relative to the normal reference sample, satisfying the following condition: ; When any of the above conditions for maintaining high output capability and the condition for significant shift in maximum phase angle are met simultaneously, the solid-state zinc-air battery to be tested is determined to be in a state of air-side mass transfer limitation risk. The criteria for determining the slight abnormal state are as follows: the solid-state zinc-air battery under test meets the high-output type determination result in step S4, and the impedance frequency response characteristics in step S5 only meet one of the following: low-frequency impedance rise, slight shift of maximum phase angle, or slight extension of Nyquist trajectory, and does not reach the determination threshold of the air-side mass transfer limited risk state. When the above conditions are met, a slight abnormality prompt is output and tracking is recommended. The criteria for determining other abnormal states of high-output type are as follows: when the quasi-solid-state zinc-air battery to be tested has been determined to be a high-output type sample, but its impedance frequency response characteristics do not meet the criteria for normal state determination, nor do they meet the criteria for air-side mass transfer limited risk state or slight abnormal state determination, or there are inconsistencies between different impedance frequency response characteristics, a high-output type other abnormality prompt will be output, and a retest suggestion will be given.

9. The method according to claim 1, characterized in that, The diagnostic conclusion in step S8 includes the status category, main criteria, auxiliary criteria, or treatment recommendations; The state categories include normal state, full cell aging state, zinc anode corrosion / salting out / passivation failure state, abnormal zinc sheet oxidation or abnormal zinc anode surface state, missing or significantly failed air electrode catalyst layer state, placement decay state, loose contact or insufficient electrode-gel interface contact state, air obstruction or air-side mass transfer limitation risk state, output-limited or output-unstable other abnormal states, slight abnormal state, and high-output other abnormal states; boundary sample type output retesting suggestion is not considered as a specific material interface state category; the main criteria include at least one of the first-level judgment characteristics described in step S1, the output capability characteristics described in step S3, and the impedance frequency response characteristics described in step S5. The auxiliary criteria refer to additional features used to verify the main criteria, distinguish similar sources of anomalies, or improve the reliability of the judgment. The processing suggestions are used to provide guidance on subsequent testing or observation methods when the characteristic quantity of the quasi-solid-state zinc-air battery under test is near the threshold, there are inconsistencies between different criteria, the curve coverage range is insufficient, or the diagnostic result is a slightly abnormal state or other abnormal state; the processing suggestions include retest suggestions and follow-up suggestions.

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