A method and device for multi-field collaborative repair of retired batteries

Abstract

The present invention discloses a method and device for multi-field coordinated repair of retired batteries, and the present invention relates to the field of battery repair technology. The method comprises the following steps: charging and discharging the retired batteries in sequence, and the charging and / or discharging are performed under the action of a coordinated field to obtain a regenerated battery; the coordinated field is at least one of a magnetic field, a pressure field or a temperature field, and the charging and discharging are cycled 1-20 times in total. The present invention solves the problems of complex existing battery recycling processes, high costs and poor effects. The present invention can restore retired batteries to more than 80% of the initial capacity of new batteries, thereby realizing the recycling of lithium-ion batteries and sodium-ion batteries. The method of the present invention does not require disassembly of batteries, is short in time, has low energy consumption, low cost, and no three wastes.

Description

Technical Field

[0001] The present invention relates to the technical field of battery repair, and in particular to a method and device for multi-field collaborative repair of retired batteries. Background Art

[0002] At present, commercial batteries include power batteries, energy storage batteries and 3C batteries according to application scenarios, mainly lithium-ion batteries and sodium-ion batteries. Among them, power batteries and 3C batteries are mainly lithium-ion batteries, and energy storage batteries are mainly sodium-ion batteries. The more mature lithium-ion battery systems include nickel-cobalt-manganese ternary positive electrode / / graphite negative electrode, nickel-cobalt-manganese ternary positive electrode / / silicon-based negative electrode, lithium cobalt oxide positive electrode / / graphite negative electrode, lithium cobalt oxide positive electrode / / silicon-based negative electrode, lithium iron phosphate positive electrode / / graphite negative electrode, lithium manganese oxide positive electrode / / graphite negative electrode, lithium-rich manganese-based positive electrode / / graphite negative electrode, etc. The next generation of lithium-ion batteries include high-nickel ternary positive electrode / / lithium metal negative electrode, lithium-rich manganese-based positive electrode / / lithium metal negative electrode, high-nickel ternary positive electrode / / phosphorus-based negative electrode, lithium-rich manganese-based positive electrode / / phosphorus-based negative electrode, etc.; sodium-ion batteries include layered oxide positive electrode / / carbon negative electrode, Prussian blue positive electrode / / carbon negative electrode, polyphosphate positive electrode / / carbon negative electrode, layered oxide positive electrode / / phosphorus-based negative electrode, Prussian blue positive electrode / / phosphorus-based negative electrode, polyphosphate positive electrode / / phosphorus-based negative electrode, etc.

[0003] The service life of power batteries is 5-8 years, that of 3C batteries is 3-5 years, and that of energy storage batteries is 5-15 years. Since 2016, the production and sales of power batteries, 3C batteries, and energy storage batteries have been increasing day by day around the world. my country's power batteries have exceeded 600GWh and are increasing rapidly. If discarded batteries are not recycled, it will have a serious impact on the natural environment. If the recycled batteries are technically extracted, many materials can be reused, and the recycling of used batteries will form a very large market. However, the current battery recycling process is very complicated, mainly based on violent disassembly methods, and there are the following problems: 1. Complex process; 2. Low recycling rate; 3. High recycling cost; 4. Long time period. Summary of the invention

[0004] In order to solve the above technical problems, the purpose of the present invention is to provide a method and device for multi-field coordinated repair of retired batteries, so as to solve the problems of complex, high cost and poor effect of existing battery recycling processes.

[0005] The technical solution of the present invention to solve the above technical problems is as follows: a method for multi-field synergistic repair of retired batteries is provided, comprising the following steps: charging and discharging the retired batteries in sequence, the charging and / or discharging being carried out under the action of a synergistic field to obtain a regenerated battery; the synergistic field is at least one of a magnetic field, a pressure field or a temperature field, and the charging and discharging are cycled 1-20 times in total.

[0006] On the basis of the above technical solution, the present invention can also be improved as follows:

[0007] Furthermore, the positive electrode material of the retired battery contains an oxide or polyphosphate of at least one of lithium, sodium, potassium, cobalt, nickel, manganese, iron, copper, titanium, vanadium, chromium and zinc, or Prussian blue or Prussian white.

[0008] Furthermore, the retired batteries are lithium-ion batteries or sodium-ion batteries.

[0009] Furthermore, the positive electrode material of the lithium-ion battery includes at least one of lithium nickel oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium-rich lithium manganese oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium manganese iron phosphate and lithium cobalt phosphate.

[0010] Furthermore, the positive electrode material of the sodium ion battery contains at least one of sodium cobaltate, sodium manganate, sodium nickelate, sodium vanadate, sodium chromium titanate, sodium manganese phosphate, sodium iron phosphate, sodium vanadium phosphate, sodium iron pyrophosphate, sodium iron sulfate, sodium copper iron manganate, sodium nickel iron manganate, sodium rich sodium manganate, Prussian blue and Prussian white.

[0011] Furthermore, the electrolyte of the retired battery is at least one of an ester electrolyte system, an ether electrolyte system, an ionic liquid electrolyte system and an aqueous electrolyte system.

[0012] Furthermore, the negative electrode material of the retired battery contains at least one of carbon, phosphorus, silicon, tin, lithium and sodium.

[0013] Furthermore, the retired batteries are soft-pack laminated batteries, steel-shell laminated batteries, blade-type batteries, cylindrical batteries or button-type batteries.

[0014] Further, charging and discharging were performed at a voltage range of 1.5-4.8V and a charge / discharge rate of 0.01-10C.

[0015] Further, charging and discharging were performed at a voltage range of 3-4.2V and a charge / discharge rate of 0.1-1C.

[0016] Further, the retired batteries are charged and discharged in sequence, the charging and / or discharging are performed under the action of a synergistic field, and the charging and discharging are cycled 20 times in total.

[0017] Further, the retired battery is charged and discharged in sequence, and the charging and / or discharging is performed under the action of a synergistic field, with one charge and one discharge being performed.

[0018] Further, the retired battery is charged and discharged in sequence, the charging and / or discharging is performed under the action of a synergistic field, and the charging and discharging are cycled 1 to 10 times in total.

[0019] Furthermore, the retired battery is charged and discharged in sequence, the charging and / or discharging is performed under the action of a synergistic field, and the charging and discharging are cycled 1-5 times in total.

[0020] Furthermore, the retired battery is charged and discharged in sequence, the charging and / or discharging is carried out under the action of a synergistic field, and the charging and discharging are cycled twice in total.

[0021] Furthermore, the retired batteries are charged and discharged in sequence, the charging and / or discharging are carried out under the action of a synergistic field, and the charging and discharging are cycled three times in total.

[0022] Furthermore, the retired batteries are charged and discharged in sequence, the charging and / or discharging are carried out under the action of a synergistic field, and the charging and discharging are cycled 5 times in total.

[0023] Furthermore, the charging and discharging time is 4-100h.

[0024] Furthermore, the time for charging and discharging is 6-20 hours.

[0025] Furthermore, the charging and discharging time was 10 h.

[0026] Furthermore, the magnetic field strength is 0.1-2T.

[0027] Furthermore, the magnetic field strength is 0.3-1T.

[0028] Furthermore, the magnetic field strength is 0.5-1T.

[0029] Furthermore, the magnetic field strength is 0.3-1.2T.

[0030] Furthermore, the magnetic field strength is 0.4T.

[0031] Furthermore, the magnetic field strength is 0.8T.

[0032] Furthermore, the magnetic field strength is 1.2T.

[0033] Furthermore, the pressure field strength is 500-5000Pa.

[0034] Furthermore, the pressure field strength is 1000Pa.

[0035] Furthermore, the temperature of the temperature field is -30°C to 80°C.

[0036] Furthermore, the temperature of the temperature field is 0°C-80°C.

[0037] Furthermore, the temperature of the temperature field is 35°C-80°C.

[0038] The present invention also provides a regenerated battery repaired by the above method.

[0039] The present invention also provides a device used in the above method, including: a retired battery, a charging and discharging instrument, a pressure field, a magnetic field and a temperature control box, the positive pole of the charging and discharging instrument is connected to the positive pole of the retired battery, the negative pole of the charging and discharging instrument is connected to the negative pole of the retired battery, the pressure field is arranged on both sides of the side wall of the retired battery, the magnetic field is arranged on the outside of the pressure field, the retired battery, the pressure field and the magnetic field are all arranged in the temperature control box, and the charging and discharging instrument is arranged outside the temperature control box.

[0040] The present invention has the following beneficial effects:

[0041] 1. How to repair the bulk structure of positive and negative electrode materials, repair the grain boundary interface, and the electrode / electrolyte interface are the key to battery regeneration applications. The present invention is a new technology for non-disassembly recycling and is the key to the reuse of retired secondary ion batteries. The present invention places the retired battery under the conditions of at least one of the magnetic field, temperature field, and force field, and performs charge and discharge activation regeneration within a certain voltage range. After several charge and discharge activations, the positive and negative electrode grains are repaired and reconstructed, so that the battery performance can be restored to more than 80% of the initial capacity of the new battery, thereby realizing the recycling of lithium-ion batteries and sodium-ion batteries. The battery regeneration method provided by the present invention has the advantages of no need to disassemble the battery, short time, low energy consumption, low cost, and no three wastes.

[0042] 2. The magnetic field, force field or temperature field of the present invention is used to change the bulk reaction process and interface reaction process of the positive electrode material and the negative electrode material of the battery; the magnetic field and temperature field are used to repair the arrangement and crystallinity of transition metal ions and alkali metal ions in the bulk phase of the positive electrode material, and repair the grain boundaries and electrode / electrolyte interface structure; the magnetic field and force field are used to repair the bulk and interface structure of the negative electrode material, and the pressure field and temperature field are used to repair the electrode micro-nano structure and activate active substances that cannot react at room temperature.

[0043] 3. The charging and discharging device of the present invention works in synergy with the magnetic field. The magnetic field regulates the bulk atomic arrangement and the electron spin state, repairs the bulk structure and the interface structure, and is mainly applicable to positive electrode materials containing metal elements (mainly for the decay or failure of the positive electrode);

[0044] The synergistic effect of the charge and discharge instrument and the pressure field can suppress volume changes and repair the electrode micro-nano structure. It is mainly applicable to metal lithium anode, metal sodium anode, phosphorus-based anode, silicon-based anode or carbon-based anode (mainly for the decline or failure of the anode);

[0045] The synergistic effect of the charge and discharge instrument and the temperature field can improve the reaction kinetics and activate active substances that cannot react at room temperature. It is mainly applicable to metal lithium anode, metal sodium anode, phosphorus-based anode, silicon-based anode, carbon-based anode, lithium iron phosphate anode that is easy to decay at low temperature, and lithium manganese oxide anode that is easy to decay at high temperature;

[0046] The charging and discharging instrument, pressure field and temperature field work together. The temperature field improves the reaction kinetics and activates the active substances in the positive electrode and / or negative electrode that cannot react at room temperature. At the same time, the pressure field suppresses the volume change and repairs the micro-nano structure of the positive electrode and / or negative electrode. It is especially suitable for metal lithium negative electrode, metal sodium negative electrode, phosphorus-based negative electrode, silicon-based negative electrode or carbon-based negative electrode (mainly for the decline or failure of the negative electrode), especially for temperature-sensitive lithium iron phosphate positive electrode;

[0047] The charging and discharging instrument, magnetic field and temperature field work together. The magnetic field regulates the bulk atomic arrangement and electron spin state, repairs the bulk structure and interface structure, and the temperature field improves the reaction kinetics and activates active substances that cannot react at room temperature. It is mainly suitable for bulk and interface repair of positive electrode materials containing metal elements (mainly for the decline or failure of the positive electrode), and is also suitable for bulk and interface repair of metal lithium negative electrodes, metal sodium negative electrodes, phosphorus-based negative electrodes, silicon-based negative electrodes, carbon-based negative electrodes, etc. (mainly for the decline or failure of the negative electrode);

[0048] The charging and discharging instrument, magnetic field and pressure field work together. The magnetic field regulates the bulk atomic arrangement and electron spin state, repairs the bulk structure and interface structure. At the same time, the pressure field suppresses volume changes and repairs the electrode micro-nano structure. It is mainly applicable to the bulk and interface repair of positive electrode materials containing metal elements (mainly for the decline or failure of the positive electrode), and is also applicable to the bulk and interface repair of metal lithium negative electrodes, metal sodium negative electrodes, phosphorus-based negative electrodes, silicon-based negative electrodes, and carbon-based negative electrodes (mainly for the decline or failure of the negative electrode).

[0049] Under the synergistic action of the charging and discharging instrument, magnetic field, force field and temperature field, the magnetic field regulates the bulk atomic arrangement and electron spin state, repairs the bulk structure and interface structure, while suppressing volume changes and repairing the electrode micro-nano structure. In addition, it improves the reaction kinetics and activates active substances that cannot react at room temperature. It is mainly suitable for the bulk and interface repair of positive electrode materials containing metal elements (mainly for the decay or failure of the positive electrode), and is also suitable for the bulk and interface repair of metal lithium negative electrodes, metal sodium negative electrodes, phosphorus-based negative electrodes, silicon-based negative electrodes, and carbon-based negative electrodes (mainly for the decay or failure of the negative electrode). BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 It is a device diagram of the present invention. DETAILED DESCRIPTION

[0051] The principles and features of the present invention are described below in conjunction with the accompanying drawings. The examples are only used to explain the present invention and are not used to limit the scope of the present invention. If specific conditions are not specified in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0052] Explanation of symbols:

[0053] The abbreviations of electrode materials in lithium batteries are as follows:

[0054] NCM: Nickel-cobalt-manganese-oxide ternary cathode

[0055] NCM622: Nickel-cobalt-lithium manganese oxide ternary positive electrode (atomic ratio of three elements is 6:2:2)

[0056] NCM9 series: high nickel content nickel cobalt manganese oxide ternary positive electrode (nickel molar content in transition metal ≥ 90%)

[0057] NCM8 series: high nickel content nickel cobalt manganese oxide ternary positive electrode (nickel molar content in transition metal ≥ 80%)

[0058] LCO: Lithium cobalt oxide cathode

[0059] LNO: Lithium Nickel Oxide

[0060] LMO: Lithium manganate

[0061] Lithium-rich LMO: Lithium-rich manganese-based cathode

[0062] LNMO: Lithium Nickel Manganese Oxide:

[0063] LFP: Lithium Iron Phosphate

[0064] LMFP: Lithium manganese iron phosphate

[0065] LCP: Lithium Cobalt Phosphate

[0066] G: Graphite negative electrode

[0067] Si: Silicon-based negative electrode

[0068] P: Phosphorus-based negative electrode

[0069] The abbreviations of the electrode materials in sodium batteries are as follows:

[0070] NFM: Nickel-iron-manganese layered oxide cathode

[0071] NVP: Sodium Vanadium Phosphate Cathode

[0072] NFP: Sodium Ferrous Phosphate

[0073] PB: Prussian blue positive electrode

[0074] NCT: Na 0.6 [Cr 0.6 Ti 0.4 ]O2 layered oxide cathode

[0075] C: Carbon-based negative electrode

[0076] P (Na) :Phosphorus-based negative electrode

[0077] The specific capacity is calculated based on the mass of the positive electrode material, and the capacity retention rate is based on the initial capacity of the new battery.

[0078] use Figure 1 The following Examples 1-17 and Comparative Examples 1-34 were carried out using the device.

[0079] Charge and discharge instrument manufacturer: Xinwei; among them, Example 8 uses the charge and discharge instrument model: CTE-4032-5V60A-NTA, and other embodiments use the charge and discharge instrument model: CT-4008Tn-5V6A-164 / S1.

[0080] Magnetic field manufacturer: Henan Huaming Instrument Equipment Co., Ltd.; Model: SBV, WD, NMR and HM series electromagnets and permanent magnets, such as SBV-100, SBV-50, WD-50, HM10020-08, etc.

[0081] Pressure field manufacturer: The pressure plate is a homemade device, and the pressure detector is from Bengbu Dayang Sensing System Engineering Co., Ltd.; Model: New energy 3C lithium battery flat pressure sensor.

[0082] Temperature field manufacturer: Shanghai Yiheng Scientific Instrument Co., Ltd.; Model: Shanghai Yiheng high and low temperature test chamber BPHS-500B, blast drying chamber DHG and other series of temperature control chambers.

[0083] Embodiment 1:

[0084] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0085] The retired battery is activated by a charge-discharge instrument and a magnetic field. The regeneration conditions are 1 charge and 1 discharge at a voltage range of 3-4.2V, a magnetic field strength of 2T, and a charge / discharge rate of 0.2C. The activation is completed (10 hours in total) to obtain a regenerated battery.

[0086] Among them, the retired battery conditions are: NCM8 series / / G (soft-pack lithium battery, n / p=1.05, 10Ah), after 50 cycles, the capacity is retained by 88%; the initial specific capacity is 208mAh / g, and the 50th specific capacity is 183mAh / g.

[0087] Embodiment 2:

[0088] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0089] The retired battery is activated by a charge-discharge instrument and a magnetic field. The regeneration conditions are 1 charge and 1 discharge at a voltage range of 3-4.5V, a magnetic field strength of 0.6T, and a charge / discharge rate of 0.01C. The activation is completed (100h in total) to obtain a regenerated battery.

[0090] Among them, the retired battery conditions are: LCO / / G (soft-pack lithium battery, n / p=1.05, 10Ah), after 300 cycles, the capacity is retained by 87%; the initial specific capacity is 168mAh / g, and the 300th specific capacity is 146mAh / g.

[0091] Embodiment 3:

[0092] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0093] The retired battery is activated by a charge-discharge instrument and a magnetic field. The regeneration conditions are 1 charge and 1 discharge at a voltage range of 2-4V, a magnetic field strength of 0.4T, and a charge / discharge rate of 0.5C. Then, 1 charge and 1 discharge are repeated 2 times to complete the activation (12 hours in total) to obtain a regenerated battery.

[0094] Among them, the retired battery conditions are: NFM / / C (soft-pack sodium battery, n / p=1.1, 5Ah), after 100 cycles, the capacity is retained by 86%; the initial specific capacity is 136mAh / g, and the 100th specific capacity is 117mAh / g.

[0095] Embodiment 4:

[0096] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0097] The retired battery is activated by a charge-discharge instrument and a pressure field. The regeneration conditions are: charge once, cancel the pressure field, discharge once, restore the pressure field, charge once, cancel the pressure field, discharge once, repeat the charge and discharge once 3 times, and then the activation is completed (50 hours in total) to obtain a regenerated battery.

[0098] Among them, the retired battery conditions are: LCP / / Li (button-type lithium battery, n / p=1.2, 2Ah), after 50 cycles, the capacity is retained at 84%; the initial specific capacity is 128mAh / g, and the 50th specific capacity is 108mAh / g.

[0099] Embodiment 5:

[0100] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0101] The retired battery was activated by using a charge-discharge instrument and a pressure field. The regeneration conditions were 1 charge and 1 discharge at a voltage range of 2.5-4.7V, a pressure field of 2000Pa, and a charge / discharge rate of 0.2C. The activation was completed (10 hours in total) to obtain a regenerated battery.

[0102] Among them, the retired battery conditions are: lithium-rich LMO / / Si (soft-pack lithium battery, n / p=1.2, 2Ah), after 50 cycles, the capacity is retained by 78%; the initial specific capacity is 217mAh / g, and the 50th specific capacity is 169mAh / g.

[0103] Embodiment 6:

[0104] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0105] The retired battery is activated by using a charge-discharge instrument and a pressure field. The regeneration conditions are to charge and discharge once at a voltage range of 2-3.8V, a pressure field of 1000Pa, and a charge / discharge rate of 0.2C. Then, the charging and discharging are repeated once, and the activation is completed (a total of 20 hours) to obtain a regenerated battery.

[0106] Among them, the retired battery conditions are: PB / / P (Na) (Soft-pack sodium battery, n / p=1.2, 2Ah), after 50 cycles, the capacity is retained by 90%; the initial specific capacity is 138mAh / g, and the 50th specific capacity is 124mAh / g.

[0107] Embodiment 7:

[0108] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0109] The retired battery is activated by using a charge-discharge instrument and a temperature field. The regeneration conditions are to charge and discharge once at a voltage range of 3-4.2V, a temperature field of 50°C, and a charge / discharge rate of 0.2C, and activation is completed (a total of 10 hours) to obtain a regenerated battery.

[0110] Among them, the retired battery conditions are: NCM622 / / Si (lithium battery 18650 type, n / p=1.1), after 50 cycles, the capacity is retained at 88%; the initial specific capacity is 182 mAh / g, and the 50th specific capacity is 160 mAh / g.

[0111] Embodiment 8:

[0112] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0113] The retired battery is activated by using a charge-discharge instrument and a temperature field. The regeneration conditions are 1 charge and 1 discharge at a voltage range of 2.5-4.5V, a temperature field of 80℃, and a charge / discharge rate of 10C. Then, 1 charge and 1 discharge are repeated 19 times to complete the activation (4h in total) to obtain a regenerated battery.

[0114] Among them, the retired battery conditions are: LMFP / / P (steel shell lithium battery, n / p=1.1, 5Ah), after 50 cycles, the capacity is retained at 85%; the initial specific capacity is 118mAh / g, and the 50th specific capacity is 100mAh / g.

[0115] Embodiment 9:

[0116] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0117] The retired battery is activated by using a charge-discharge instrument and a temperature field. The regeneration conditions are: one charge and one discharge at a voltage range of 2.2-3.8V, a temperature field of 40°C, and a charge / discharge rate of 0.1C. The activation is completed (a total of 20 hours) to obtain a regenerated battery.

[0118] Among them, the retired battery conditions are: NVP / / P (Na) (Sodium battery), after 50 cycles, the capacity is retained at 88%; the initial specific capacity is 106 mAh / g, and the 50th specific capacity is 93 mAh / g.

[0119] Embodiment 10:

[0120] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0121] The retired battery is activated by using a charge-discharge instrument, magnetic field and temperature field. The regeneration conditions are 3-4.2V voltage range, 1T magnetic field intensity, 40℃ temperature field, 0.2C charge / discharge rate, 1 charge and 1 discharge, that is, activation is completed (a total of 10 hours), and a regenerated battery is obtained;

[0122] Among them, the retired battery conditions are: LNO / / Si (steel shell lithium battery, n / p=1.05, 5Ah), after 50 cycles, the capacity is retained at 85%; the initial specific capacity is 148mAh / g, and the 50th specific capacity is 126mAh / g.

[0123] Embodiment 11:

[0124] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0125] The retired battery is activated by using a charge and discharge instrument, a magnetic field and a temperature field. The regeneration conditions are: one charge and one discharge at a voltage range of 2.5-4.7V, a magnetic field strength of 0.1T, a temperature field of -30℃, and a charge / discharge rate of 0.2C. Then, one charge and one discharge are repeated once, and activation is completed (a total of 20 hours) to obtain a regenerated battery.

[0126] Among them, the retired battery conditions are: lithium-rich LMO / / G (soft-pack lithium battery, n / p=1.2, 2Ah), after 50 cycles, the capacity is retained by 80%; the initial specific capacity is 218mAh / g, and the 50th specific capacity is 174mAh / g.

[0127] Embodiment 12:

[0128] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0129] The retired battery is activated by using a charge-discharge instrument, a magnetic field and a temperature field. The regeneration conditions are 1.5-3V voltage range, 0.1T magnetic field intensity, 80℃ temperature field, 1C charge / discharge rate, 1 charge and 1 discharge, and then 1 charge and 1 discharge are repeated 9 times, that is, the activation is completed (a total of 20 hours), and a regenerated battery is obtained;

[0130] Among them, the conditions for retired batteries are: NCT / / P (Na) (Soft-pack sodium battery, n / p=1.1, 2Ah), after 50 cycles, the capacity is retained by 84%; the initial specific capacity is 75mAh / g, and the 50th specific capacity is 63mAh / g.

[0131] Embodiment 13:

[0132] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0133] The retired battery is activated by using a charge and discharge instrument, a magnetic field and a pressure field. The regeneration conditions are: under a voltage range of 3-4.3V, a magnetic field intensity of 0.8T, a pressure field of 500Pa, and a charge / discharge rate of 0.1C, the magnetic field and pressure field are cancelled for one charge, and the magnetic field and pressure field are restored for one discharge, and the activation is completed (a total of 20 hours), and a regenerated battery is obtained;

[0134] Among them, the retired battery conditions are: NCM9 series / / Li (soft-pack lithium battery, n / p=1.2, 2Ah), after 100 cycles, the capacity is retained by 80%; the initial specific capacity is 220mAh / g, and the 100th specific capacity is 176mAh / g.

[0135] Embodiment 14:

[0136] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0137] The retired battery is activated by using a charge-discharge instrument, a magnetic field and a pressure field. The regeneration conditions are to charge and discharge once at a voltage range of 1.5-3.8V, a magnetic field intensity of 0.3T, a pressure field of 1000Pa, and a charge / discharge rate of 0.2C, and activation is completed (a total of 10 hours) to obtain a regenerated battery;

[0138] Among them, the retired battery conditions are: NFP / / Na (soft-pack sodium battery, n / p=1.1, 2Ah), after 50 cycles, the capacity is retained by 83%; the initial specific capacity is 125mAh / g, and the 50th specific capacity is 104mAh / g.

[0139] Embodiment 15:

[0140] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0141] The retired battery is activated by using a charge-discharge instrument, a temperature field and a pressure field. The regeneration conditions are to charge and discharge once at a voltage range of 2.2-4V, a temperature field of 40°C, a pressure field of 3000Pa, and a charge / discharge rate of 0.5C, and activation is completed (a total of 10 hours) to obtain a regenerated battery;

[0142] Among them, the retired battery conditions are: LFP / / Li (blade-shaped lithium battery, n / p=1.1, 5Ah), after 50 cycles, the capacity is retained at 91%; the initial specific capacity is 144mAh / g, and the 50th specific capacity is 131mAh / g.

[0143] Embodiment 16:

[0144] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0145] The retired battery is activated by using a charge and discharge instrument, temperature field and pressure field. The regeneration conditions are 1 charge and 1 discharge at a voltage range of 2.7-4.3V, a temperature field of 0℃, a pressure field of 2000Pa, and a charge / discharge rate of 0.1C. The activation is completed (20h in total) to obtain a regenerated battery.

[0146] Among them, the retired battery conditions are: LMO / / G (lithium battery, n / p=1.1, 1Ah), after 50 cycles, the capacity is retained at 88%; the initial specific capacity is 106mAh / g, and the 50th specific capacity is 93mAh / g.

[0147] Embodiment 17:

[0148] A method for multi-field collaborative repair of retired batteries, comprising the following steps:

[0149] The retired battery is activated by a charging and discharging instrument, a magnetic field, a temperature field and a pressure field. The regeneration conditions are 1 charge and 1 discharge at a voltage range of 3-4.2V, a magnetic field strength of 1.2T, a temperature field of 35°C, a pressure field of 2500Pa and a charge / discharge rate of 0.2C. The activation is completed (10 hours in total) to obtain a regenerated battery.

[0150] Among them, the retired battery conditions are: NCM8 series / / Si (soft-pack lithium battery, n / p=1.1, 10Ah), after 50 cycles, the capacity is retained at 85%; the initial specific capacity is 204mAh / g, and the 50th specific capacity is 173mAh / g.

[0151] Comparative Example 1-2:

[0152] A method for repairing a retired battery comprises the following steps:

[0153] Only the charging and discharging instrument and the magnetic field are used, and the rest is the same as in Example 1.

[0154] Comparative Examples 3-4:

[0155] A method for repairing a retired battery comprises the following steps:

[0156] Only the charging and discharging instrument and the magnetic field are used, and the rest is the same as in Example 2.

[0157] Comparative Examples 5-6:

[0158] A method for repairing a retired battery comprises the following steps:

[0159] Only the charging and discharging instrument and the magnetic field are used, and the rest is the same as in Example 3.

[0160] Comparative Examples 7-8:

[0161] A method for repairing a retired battery comprises the following steps:

[0162] Only the charge and discharge instrument and the pressure field (time is 25h) are used respectively, and the rest is the same as in Example 4. Comparative Examples 9-10:

[0163] A method for repairing a retired battery comprises the following steps:

[0164] Only the charge and discharge instrument and the pressure field are used, and the rest is the same as in Example 5.

[0165] Comparative Examples 11-12:

[0166] A method for repairing a retired battery comprises the following steps:

[0167] Only the charge and discharge instrument and the pressure field are used, and the rest is the same as in Example 6.

[0168] Comparative Examples 13-14:

[0169] A method for repairing a retired battery comprises the following steps:

[0170] Only the charge and discharge instrument and the temperature field are used, and the rest is the same as in Example 7.

[0171] Comparative Examples 15-16:

[0172] A method for repairing a retired battery comprises the following steps:

[0173] Only the charge and discharge instrument and the temperature field are used, and the rest is the same as in Example 8.

[0174] Comparative Examples 17-18:

[0175] A method for repairing a retired battery comprises the following steps:

[0176] Only the charge and discharge instrument and the temperature field are used, and the rest is the same as in Example 9.

[0177] Comparative Examples 19-20:

[0178] A method for repairing a retired battery comprises the following steps:

[0179] Only a charge and discharge instrument, only a magnetic field and a temperature field are used respectively, and the rest is the same as in Example 10.

[0180] Comparative Examples 21-22:

[0181] A method for repairing a retired battery comprises the following steps:

[0182] Only a charge and discharge instrument, only a magnetic field and a temperature field are used respectively, and the rest is the same as in Example 11.

[0183] Comparative Examples 23-24:

[0184] A method for repairing a retired battery comprises the following steps:

[0185] Only a charge and discharge instrument, only a magnetic field and a temperature field are used respectively, and the rest is the same as in Example 12.

[0186] Comparative Examples 25-26:

[0187] A method for repairing a retired battery comprises the following steps:

[0188] Only a charge and discharge instrument, only a magnetic field and a pressure field are used (for 10 hours), and the rest is the same as in Example 13.

[0189] Comparative Examples 27-28:

[0190] A method for repairing a retired battery comprises the following steps:

[0191] Only a charge and discharge instrument, only a magnetic field and a pressure field are used respectively, and the rest is the same as in Example 14.

[0192] Comparative Examples 29-30:

[0193] A method for repairing a retired battery comprises the following steps:

[0194] Only a charge and discharge instrument, only a pressure field and a temperature field are used respectively, and the rest is the same as in Example 15.

[0195] Comparative Examples 31-32:

[0196] A method for repairing a retired battery comprises the following steps:

[0197] Only a charge and discharge instrument, only a pressure field and a temperature field are used respectively, and the rest is the same as Example 16.

[0198] Comparative Examples 33-34:

[0199] A method for repairing a retired battery comprises the following steps:

[0200] Only a charge and discharge instrument, only a magnetic field, a pressure field and a temperature field are used respectively, and the rest is the same as Example 17.

[0201] Test example

[0202] 1. The performance of the regenerated batteries repaired in Example 1-17 and Comparative Example 1-34 was tested. The results are shown in Table 1.

[0203] Table 1 Battery specific capacity (mAh / g) and retention rate after cycling

[0204]

[0205]

[0206]

[0207] It can be seen from Table 1 that the method of the present invention can effectively realize the repair and regeneration of retired batteries.

[0208] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for multi-field collaborative repair of retired batteries, characterized in that: The method comprises the following steps: sequentially charging and discharging the retired battery, wherein the charging and / or discharging is performed under the action of a synergistic field, to obtain a regenerated battery; The synergistic field is at least two of a magnetic field, a pressure field and a temperature field, and the charging and discharging are cycled 1 to 20 times in total; The positive electrode material of the retired battery comprises an oxide or polyphosphate of at least one of lithium, sodium, potassium, cobalt, nickel, manganese, iron, copper, titanium, vanadium, chromium and zinc, or Prussian blue or Prussian white; The retired battery is a lithium-ion battery or a sodium-ion battery; The magnetic field strength is 0.3-1T; The pressure field strength is 500-5000Pa; The temperature of the temperature field is -30°C to 80°C; Charging and discharging were performed in the voltage range of 1.5-4.8V and the charge / discharge rate of 0.01-10C.

2. The method for multi-field coordinated repair of retired batteries according to claim 1, characterized in that: The retired battery electrolyte is at least one of an ester electrolyte system, an ether electrolyte system, an ionic liquid electrolyte system and an aqueous electrolyte system.

3. The method for multi-field coordinated repair of retired batteries according to claim 1, characterized in that: The negative electrode material of the retired battery contains at least one of carbon, phosphorus, silicon, tin, lithium and sodium.

4. A regenerated battery repaired by the method for repairing retired batteries with multiple fields as described in any one of claims 1 to 3.

5. The device used in the method for multi-field coordinated repair of retired batteries according to any one of claims 1 to 3 is characterized in that: include: Retired batteries, a charging and discharging instrument, a pressure field, a magnetic field and a temperature control box, wherein the positive pole of the charging and discharging instrument is connected to the positive pole of the retired battery, the negative pole of the charging and discharging instrument is connected to the negative pole of the retired battery, the pressure field is arranged on both sides of the side wall of the retired battery, the magnetic field is arranged outside the pressure field, the retired batteries, the pressure field and the magnetic field are all arranged in the temperature control box, and the charging and discharging instrument is arranged outside the temperature control box.

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