Thermoelectric potential improved thermal regeneration electrochemical cycle battery based on thermosensitive crystallization and use method thereof

Abstract

The invention belongs to the technical field of thermoelectric chemical conversion, and particularly relates to a thermal electromotive force-improved charging-free thermal regeneration electrochemical cycle battery based on thermosensitive crystallization and a using method of the thermal electromotive force-improved charging-free thermal regeneration electrochemical cycle battery based on thermosensitive crystallization. The thermal electromotive force-improved charging-free thermal regeneration electrochemical cycle battery comprises a positive electrode, a negative electrode, a positive electrode electrolyte, a negative electrode electrolyte and a cation exchange membrane, the electrode potentials in the positive electrode electrolyte and the negative electrode electrolyte are equal at an intermediate temperature, the battery voltage is 0V, the positive electrode electrolyte and / or the negative electrode electrolyte also contain an additive for inducing thermosensitive crystallization of oxidizing ions or reducing ions in the electrolyte, and the additive induces the oxidizing ions or reducing ions to be dissolved at a first temperature and crystallized at a second temperature, the thermoelectric force of the battery is improved through the thermosensitive crystallization process. The thermal regeneration electrochemical cycle battery provided by the invention does not need electric power assistance, and can discharge at both high temperature and low temperature; the thermal electromotive force of the battery based on the thermosensitive crystallization effect is relatively high, so that the working voltage, the capacity and the thermoelectric conversion efficiency of the battery are improved, and efficient recovery and conversion of low-grade heat are realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermo-electrochemical conversion, and in particular relates to a non-chargeable thermal regeneration electrochemical cycle battery with enhanced thermoelectric potential based on thermosensitive crystals and a method of using the battery. Background Art

[0002] Low-grade waste heat (<100℃) is widely present in the environment, industrial power plants, solar energy and geothermal energy. Recycling this kind of low-grade thermal energy helps to reduce carbon emissions, but due to its dispersed distribution and small temperature difference with the environment, efficient recycling of this low-grade heat is very difficult. In recent years, electrochemical thermo-electric conversion devices with high ion thermoelectric potential, including thermal diffusion ion capacitors, thermal batteries, and thermal regeneration electrochemical cycles (TRECs), have been proposed for the recovery of low-grade thermal energy. Among these technologies, TREC cells show great application potential due to their ability to achieve a high Carnot relative efficiency of more than 10%. TREC cells are isothermal devices whose working principle is based on the temperature dependence of the anode and cathode electrodes and their open circuit voltage V oc The change with temperature is defined as the battery thermoelectric potential α cell :

[0003]

[0004] Where E + and E - are the potentials of the positive and negative electrode reaction pairs respectively; α + and α - are the thermoelectric potentials of the positive and negative electrode reactions, respectively. Therefore, the TREC battery can convert the temperature difference into electrical output by performing charge and discharge cycles at different temperatures. However, this process requires electricity to assist the battery to regenerate. The ideal TREC battery for recovering low-grade heat is to regenerate only by thermal energy. The non-rechargeable TREC battery does not require power assistance. However, the working process of the non-rechargeable TREC battery is achieved by limiting the voltage and capacity range, thereby limiting the energy output. In order to obtain the best energy output, a larger battery thermoelectric potential is preferred. However, the thermoelectric potential of the non-rechargeable TREC batteries reported so far is generally less than 2mV / K. For example, the positive and negative electrode pairs are Fe(CN)6 3- / Fe(CN)6 4- The thermoelectric potential of the uncharged TREC battery with Prussian blue is only -1.45mV / K, based on I3 - / I - (+)||Fe(CN)6 3- / Fe(CN)6 4- The thermoelectric potential of the uncharged TREC battery is 1.8 mV / K. The recently proposed Fe(CN)6 3 / Fe(CN)6 4-The thermoelectric potential of the (+)||FePO4 / LiFePO4(-)-based non-rechargeable TREC battery is also only -1.84mV / K, which leads to low thermoelectric conversion efficiency of the non-rechargeable devices reported so far. Therefore, the development of non-rechargeable TREC batteries with high thermoelectric potential is the key to improving battery energy output and thermoelectric conversion efficiency. Summary of the invention

[0005] In view of the above defects or improvement needs of the prior art, the present invention provides a rechargeable thermal regeneration electrochemical cycle battery with improved thermoelectric potential based on thermosensitive crystals and a method of use, so as to solve the problems of low thermoelectric potential, low capacity utilization, limited energy output and low thermoelectric conversion efficiency existing in the current rechargeable thermal regeneration electrochemical cycle battery, and achieve the technical effect of efficient recovery and conversion of low-grade heat without the need for electrical assistance.

[0006] According to a first aspect of the present invention, a charge-free thermal regeneration electrochemical cycle battery with enhanced thermoelectric potential based on thermosensitive crystals is provided, wherein the thermal regeneration electrochemical cycle battery comprises a positive electrode, a negative electrode, a positive electrode electrolyte, a negative electrode electrolyte and a cation exchange membrane; the electrode potential of the redox couple in the positive electrode electrolyte and the negative electrode electrolyte is at an intermediate temperature T m The positive electrode electrolyte and / or the negative electrode electrolyte further contain an additive for inducing thermosensitive crystallization of oxidizing ions or reducing ions in the electrolyte, wherein the additive induces the oxidizing ions or reducing ions to dissolve at a first temperature T1 and to crystallize and precipitate at a second temperature T2; the battery thermoelectric potential is increased by the thermosensitive crystallization process;

[0007] The intermediate temperature T m The electrode potentials of the positive electrolyte and the negative electrolyte at different temperatures are calibrated respectively, and a curve of the relationship between the electrode potential of the positive electrolyte and the temperature and a curve of the relationship between the electrode potential of the negative electrolyte and the temperature are drawn. The temperature at the intersection of the curve of the relationship between the electrode potential of the positive electrolyte and the temperature and the curve of the relationship between the electrode potential of the negative electrolyte and the temperature is recorded as the intermediate temperature T m The temperature at which the crystalline precipitate is completely dissolved is the first temperature T1; the T m , T1, T2 in degrees Celsius all satisfy: T1>T m , T2=2T m -T1.

[0008] Preferably, when the active material in the positive electrode electrolyte is K3Fe(CN)6 / K4Fe(CN)6, the active material in the negative electrode electrolyte is KFe Ⅱ Fe Ⅲ(CN)6 (Prussian blue); when the active substance in the positive electrode electrolyte is KI3 / KI, the active substance in the negative electrode electrolyte is K3Fe(CN)6 / K4Fe(CN)6.

[0009] Preferably, when the active substance in the positive electrode electrolyte is K3Fe(CN)6 / K4Fe(CN)6, the additive is a salt containing guanidine ion, tetraethylammonium ion or 1-ethyl-3-methylimidazolium cation, or an organic solvent of ethanol, methanol or acetonitrile; when the active substance in the positive electrode electrolyte is KI3 / KI, the additive is cesium chloride or α-cyclodextrin.

[0010] Preferably, the salt containing guanidine ions is guanidine hydrochloride, guanidine sulfate or guanidine nitrate; the salt containing tetraethylammonium ions is tetraethylammonium chloride or tetraethylammonium bromide; the salt containing 1-ethyl-3-methylimidazolium ions is 1-ethyl-3-methylimidazolium chloride.

[0011] Preferably, the battery is a static battery or a flow battery.

[0012] Preferably, when the battery is the liquid flow battery, the positive electrode and the negative electrode are respectively provided with electrolyte flow channels, and the electrolyte flow channels are serpentine flow channels, comb-shaped flow channels, or spiral flow channels.

[0013] According to another aspect of the present invention, a method for using the recharge-free thermal regeneration electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals is provided, and the specific operation steps are as follows:

[0014] (1) Calibrate the electrode potentials of the positive electrolyte and the negative electrolyte at different temperatures respectively, and draw a curve of the relationship between the electrode potential of the positive electrolyte and the temperature, and a curve of the relationship between the electrode potential of the negative electrolyte and the temperature, and record the temperature at the intersection of the curve of the relationship between the electrode potential of the positive electrolyte and the temperature and the curve of the relationship between the electrode potential of the negative electrolyte and the temperature as the intermediate temperature T m ;

[0015] (2) The temperature at which the crystal precipitate in the positive electrode electrolyte or the negative electrode electrolyte is completely dissolved is referred to as the first temperature T1, and the temperature at which the crystal precipitate in the positive electrode electrolyte or the negative electrode electrolyte is precipitated is referred to as the second temperature T2; m , T1, T2 in degrees Celsius all satisfy: T1>T m , T2=2T m -T1, determining that the operating temperature range of the battery is from T2 to T1;

[0016] (3) The difference between the slope of the positive electrode electrolyte electrode potential and temperature curve and the slope of the negative electrode electrolyte electrode potential and temperature curve is recorded as the battery thermoelectric potential. The battery is kept at the intermediate temperature T mWhen the battery thermoelectric potential is greater than zero, the temperature is lowered to T2, at which time the battery voltage is negative, the positive and negative electrodes of the battery are switched, and then the battery is discharged until the battery voltage is 0V, and the battery is short-circuited after the discharge is completed;

[0017] (4) Switch the positive and negative electrodes of the battery again, then heat the battery to T1, discharge it again until the battery voltage is 0 V, and short-circuit the battery after the discharge is completed. Repeat steps (3) and (4) in this way.

[0018] According to another aspect of the present invention, a method for using the recharge-free thermal regeneration electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals is provided, and the specific operation steps are as follows:

[0019] S1 calibrates the electrode potentials of the positive electrolyte and the negative electrolyte at different temperatures, and draws a curve of the relationship between the electrode potential of the positive electrolyte and the temperature, and a curve of the relationship between the electrode potential of the negative electrolyte and the temperature, and the temperature at the intersection of the curve of the relationship between the electrode potential of the positive electrolyte and the temperature and the curve of the relationship between the electrode potential of the negative electrolyte and the temperature is recorded as the intermediate temperature T m ;

[0020] S2 denotes the temperature at which the crystal precipitate in the positive electrode electrolyte or the negative electrode electrolyte is completely dissolved as the first temperature T1, and the temperature at which the crystal precipitate in the positive electrode electrolyte or the negative electrode electrolyte is precipitated as the second temperature T2; m , T1, T2 in degrees Celsius all satisfy: T1>T m , T2=2T m -T1, determining that the operating temperature range of the battery is from T2 to T1;

[0021] S3: The difference between the slope of the positive electrolyte electrode potential and temperature curve and the slope of the negative electrolyte electrode potential and temperature curve is the battery thermoelectric potential. The battery is kept at the intermediate temperature T m When the battery thermoelectric potential is less than zero, the temperature is raised to a first temperature T1, at which time the battery voltage is negative, the positive and negative electrodes of the battery are switched, and then the battery is discharged until the battery voltage is 0V, and the battery is short-circuited after the discharge is completed;

[0022] S4 then cools the battery to a second temperature T2 and discharges the battery again until the battery voltage is 0V. After the discharge is completed, the battery is short-circuited, and steps S3 and S4 are repeated.

[0023] In general, the above technical solution conceived by the present invention has the following technical advantages compared with the prior art:

[0024] 1. The thermal regeneration electrochemical cycle battery proposed in the present invention does not require power assistance. By matching the standard electrode potentials of the positive and negative redox pairs, the voltage of the thermal regeneration electrochemical cycle battery is 0V at the intermediate temperature. In this way, both heating and cooling will generate non-zero electromotive force, so that discharge can be achieved at high and low temperatures, and the direction of the current is opposite. In this way, a charge-free thermal regeneration electrochemical cycle is achieved.

[0025] 2. The positive electrode electrolyte and / or the negative electrode electrolyte of the present invention further contains an additive, which can induce the oxidizing ions or reducing ions in the positive electrode electrolyte and / or the negative electrode electrolyte to crystallize and precipitate at low temperatures and dissolve at high temperatures. This thermosensitive crystallization effect enhances the reaction entropy change of the redox couple, so that the thermoelectric potential of the battery is higher, which increases the operating voltage and capacity of the battery, thereby improving the energy output and thermoelectric conversion efficiency of the battery.

[0026] 3. The recharge-free thermal regeneration electrochemical cycle battery with enhanced thermoelectric potential based on thermosensitive crystals of the present invention has universal applicability. In addition to being applied to static batteries, it can also be used to construct flow batteries, thereby further improving the power and efficiency of the thermal regeneration electrochemical cycle battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic structural diagram of a charge-free thermal regeneration electrochemical cycle battery with enhanced thermoelectric potential based on thermosensitive crystals provided by the present invention.

[0028] Figure 2 It is the electrode potential-temperature curve of the positive and negative electrolytes of the charge-free thermal regeneration electrochemical cycle battery provided by the present invention.

[0029] Figure 3 The additive provided by the present invention has shown the effect of Fe(CN)6 3- / Fe(CN)6 4- The thermoelectric potential is the slope of the electrode potential-temperature curve.

[0030] Figure 4 It is a picture of the negative electrode electrolyte provided by Example 1 of the present invention at 25°C and 55°C, wherein the precipitate at 55°C is completely dissolved.

[0031] Figure 5 (a) is a temperature-entropy diagram of thermal regeneration electrochemical cycle based on thermosensitive crystallization enhancement; (b) is a comparison diagram of charge-free thermal regeneration electrochemical cycle of batteries with and without guanidine salts.

[0032] Figure numerals: 1. current collector; 2. positive electrode electrolyte; 3. negative electrode electrolyte; 4. crystal precipitation; 5. positive electrode; 6. negative electrode; 7. liquid storage tank; 8. screw; 9. cation exchange membrane. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0034] According to a first aspect of the present invention, a charge-free thermal regeneration electrochemical cycle battery with enhanced thermoelectric potential based on thermosensitive crystals is provided, wherein the thermal regeneration electrochemical cycle battery comprises a positive electrode, a negative electrode, a positive electrode electrolyte, a negative electrode electrolyte and a cation exchange membrane; the electrode potential of the redox couple in the positive electrode electrolyte and the negative electrode electrolyte is at an intermediate temperature T m The positive electrode electrolyte and / or the negative electrode electrolyte further contain an additive for inducing thermosensitive crystallization of oxidizing ions or reducing ions in the electrolyte, wherein the additive induces the oxidizing ions or reducing ions to dissolve at a first temperature T1 and to crystallize and precipitate at a second temperature T2; the battery thermoelectric potential is increased by the thermosensitive crystallization process;

[0035] The intermediate temperature T m The electrode potentials of the positive electrolyte and the negative electrolyte at different temperatures are calibrated respectively, and a curve of the relationship between the electrode potential of the positive electrolyte and the temperature and a curve of the relationship between the electrode potential of the negative electrolyte and the temperature are drawn. The temperature at the intersection of the curve of the relationship between the electrode potential of the positive electrolyte and the temperature and the curve of the relationship between the electrode potential of the negative electrolyte and the temperature is recorded as the intermediate temperature T m The temperature at which the crystalline precipitate is completely dissolved is the first temperature T1; the T m , T1, T2 in degrees Celsius all satisfy: T1>T m , T2=2T m -T1.

[0036] In some embodiments, when the positive electrode electrolyte is a mixture of K3Fe(CN)6 and K4Fe(CN)6, the negative electrode electrolyte is KFe Ⅱ Fe Ⅲ (CN)6; when the positive electrode electrolyte is a mixture of KI3 and KI, the negative electrode electrolyte is a mixture of K3Fe(CN)6 and K4Fe(CN)6.

[0037] In some embodiments, the additive is a salt containing guanidine ion, tetraethylammonium ion or 1-ethyl-3-methylimidazolium cation, or an organic solvent such as ethanol, methanol or acetonitrile, cesium chloride and α-cyclodextrin.

[0038] In some embodiments, the salt containing guanidine ions is guanidine hydrochloride, guanidine sulfate or guanidine nitrate; the salt containing tetraethylammonium ions is tetraethylammonium chloride or tetraethylammonium bromide; the salt containing 1-ethyl-3-methylimidazolium ions is 1-ethyl-3-methylimidazolium chloride.

[0039] In some embodiments, the positive electrode electrolyte and the negative electrode electrolyte further contain KCl supporting electrolyte.

[0040] In some embodiments, the battery is a static battery or a flow battery.

[0041] In some embodiments, when the battery is a liquid flow battery, the positive and negative electrodes of the battery are respectively provided with electrolyte flow channels to ensure efficient flow of the electrolyte.

[0042] In some embodiments, the electrolyte flow channel is a serpentine flow channel, a comb-shaped flow channel, or a spiral flow channel.

[0043] In some embodiments, the positive electrode and the negative electrode are selected from platinum sheet, graphite felt, carbon paper, carbon cloth, carbon nanotubes, and Prussian blue.

[0044] In some embodiments, the cation exchange membrane is selected from the group consisting of Nafion series, Fumasep series, and Selemion series.

[0045] Example 1

[0046] A non-chargeable thermally regenerated electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals, the structure of which is as follows Figure 1 As shown. KI3 / KI and K3Fe(CN)6 / K4Fe(CN)6 with similar standard electrode potentials were selected as the positive and negative electrolytes, respectively. Guanidine hydrochloride (GdmCl) was added to the negative electrolyte to induce the thermosensitive crystallization of K4Fe(CN)6 to enhance the Fe(CN)6 3- / Fe(CN)6 4- Thermoelectric potential, guanidine hydrochloride with the same concentration as that of the negative electrode is added to the positive electrode electrolyte to balance the guanidine ion concentration. The concentration of the positive and negative electrode electrolytes is based on Figure 2 The temperature curve relationship of the electrode potential of the two is determined, where the positive electrode electrolyte is 0.1MKI3, 0.9MKI and 2M GdmCl, the negative electrode electrolyte is 0.3M K3Fe(CN)6, 0.3M K4Fe(CN)6 and 2M GdmCl, and the corresponding intermediate temperature is 40°C. The ion exchange membrane uses Nafion 115 (purchased from Suzhou Shengernuo Technology Co., Ltd.).

[0047] In order to demonstrate the effect of thermosensitive crystallization on the Fe(CN)6 3- / Fe(CN)6 4- The enhancement of thermoelectric potential, Figure 3The temperature dependence of the electrode potential of K3Fe(CN)6 / K4Fe(CN)6 with and without GdmCl was compared. The linear fitting showed that the thermoelectric potential of the baseline system without guanidine salt was only -1.29 mV / K, while that of Fe(CN)6 with guanidine salt was 3- / Fe(CN)6 4- The average thermoelectric potential can be as high as -3.41mV / K, especially in the temperature range of less than 20-40℃, it can even reach -4.13mV / K. In addition, we observed that the K4Fe(CN)6 precipitate can be completely dissolved at 55℃, achieving regeneration ( Figure 4 ). Based on this and referring to the intermediate temperature of 40°C, the working temperature range of 25 to 55°C was used to perform a non-chargeable thermal regeneration electrochemical cycle on the thermosensitive crystallization enhanced battery, and compared with the case of a benchmark system without guanidine salt. The working process of the non-chargeable thermal regeneration electrochemical cycle battery is: the battery thermoelectric potential α cell >0, first cool down to 25℃, at which time the battery voltage is negative, switch the positive and negative poles of the battery, then discharge until the battery voltage is 0V, short-circuit for a period of time after the discharge until the battery voltage is close to 0V, switch the positive and negative poles of the battery again, and then heat the battery to 55℃ until the voltage stabilizes and then discharge again until the battery voltage is 0V, short-circuit for a period of time after the discharge until the battery voltage is close to 0V, and repeat the operation in this way. The working principle and working process of the non-charging thermal regeneration electrochemical cycle are as follows Figure 5 As shown in (a), the additional entropy change contributed by the dissolution of K4Fe(CN)6 during heating and the precipitation of K4Fe(CN)6 during cooling and charging increases the power output of the battery, where the total power output of the battery is Figure 5 (b) The area enclosed by the discharge curve and the x-axis. The total energy density of the non-chargeable thermal regeneration electrochemical cycle battery in Example 1 is calculated to be 3.3 J / mL, and the Carnot relative efficiency of the battery is calculated to be 26.9% according to the thermal-electric conversion efficiency formula of the battery, of which the heat recovery efficiency is 70%, which are 4.6 times that of the benchmark system without guanidine salt.

[0048] It will be easily understood by those skilled in the art that 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 and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A non-chargeable thermal regeneration electrochemical cycle battery based on the thermoelectric potential enhancement of thermosensitive crystals, characterized in that: The thermal regeneration electrochemical cycle battery comprises a positive electrode, a negative electrode, a positive electrode electrolyte, a negative electrode electrolyte and a cation exchange membrane; the electrode potential of the redox couple in the positive electrode electrolyte and the negative electrode electrolyte is at an intermediate temperature T m The positive electrode electrolyte and / or the negative electrode electrolyte further contain an additive for inducing thermosensitive crystallization of oxidizing ions or reducing ions in the electrolyte, wherein the additive induces the oxidizing ions or reducing ions to dissolve at a first temperature T1 and to crystallize and precipitate at a second temperature T2; the battery thermoelectric potential is increased by the thermosensitive crystallization process; Wherein, the intermediate temperature T m The electrode potentials of the positive electrolyte and the negative electrolyte at different temperatures are calibrated respectively, and a curve of the relationship between the electrode potential of the positive electrolyte and the temperature and a curve of the relationship between the electrode potential of the negative electrolyte and the temperature are drawn. The temperature at the intersection of the curve of the relationship between the electrode potential of the positive electrolyte and the temperature and the curve of the relationship between the electrode potential of the negative electrolyte and the temperature is recorded as the intermediate temperature T m The temperature at which the crystalline precipitate is completely dissolved is the first temperature T1; the T m , T1, T2 in degrees Celsius all satisfy: T1>T m , T2=2T m -T1.

2. A non-chargeable thermal regeneration electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals according to claim 1, characterized in that: The active material in the positive electrode electrolyte and the negative electrode electrolyte is selected from K3Fe(CN)6 / K4Fe(CN)6(+)||KFe Ⅱ Fe Ⅲ (CN)6(-) or KI3 / KI(+)||K3Fe(CN)6 / K4Fe(CN)6(-).

3. A non-chargeable thermal regeneration electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals according to claim 2, characterized in that: When the active substance in the positive electrode electrolyte is K3Fe(CN)6 / K4Fe(CN)6, the additive is a salt containing guanidine ion, tetraethylammonium ion or 1-ethyl-3-methylimidazolium cation, or an organic solvent of ethanol, methanol or acetonitrile; when the active substance in the positive electrode electrolyte is KI3 / KI, the additive is cesium chloride or α-cyclodextrin.

4. A non-chargeable thermal regeneration electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals according to claim 3, characterized in that: The salt containing guanidine ions is guanidine hydrochloride, guanidine sulfate or guanidine nitrate; the salt containing tetraethylammonium ions is tetraethylammonium chloride or tetraethylammonium bromide; the salt containing 1-ethyl-3-methylimidazolium cation is 1-ethyl-3-methylimidazolium chloride.

5. A non-chargeable thermal regeneration electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals according to claim 1, characterized in that: The battery is a static battery or a flow battery.

6. A non-chargeable thermal regeneration electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals according to claim 5, characterized in that: When the battery is a liquid flow battery, the positive electrode and the negative electrode are respectively provided with electrolyte flow channels, and the electrolyte flow channels are serpentine flow channels, comb-shaped flow channels, or spiral flow channels.

7. A method for using a non-chargeable thermal regeneration electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) Calibrate the electrode potentials of the positive electrolyte and the negative electrolyte at different temperatures respectively, and draw a curve of the relationship between the electrode potential of the positive electrolyte and the temperature, and a curve of the relationship between the electrode potential of the negative electrolyte and the temperature, and record the temperature at the intersection of the curve of the relationship between the electrode potential of the positive electrolyte and the temperature and the curve of the relationship between the electrode potential of the negative electrolyte and the temperature as the intermediate temperature T m ; (2) The temperature at which the crystal precipitate in the positive electrode electrolyte or the negative electrode electrolyte is completely dissolved is referred to as the first temperature T1, and the temperature at which the crystal precipitate in the positive electrode electrolyte or the negative electrode electrolyte is precipitated is referred to as the second temperature T2; m , T1, T2 in degrees Celsius all satisfy: T1>T m , T2=2T m -T1, determining that the operating temperature range of the battery is from T2 to T1; (3) The difference between the slope of the positive electrode electrolyte electrode potential and temperature curve and the slope of the negative electrode electrolyte electrode potential and temperature curve is recorded as the battery thermoelectric potential; the battery is placed at the intermediate temperature T m When the battery thermoelectric potential is greater than zero, the temperature is lowered to a second temperature T2, at which time the battery voltage is negative, the positive and negative electrodes of the battery are switched, and then the battery is discharged until the battery voltage is 0V, and the battery is short-circuited after the discharge is completed; (4) Switching the positive and negative electrodes of the battery again, then heating the battery to the first temperature T1, and discharging the battery again until the battery voltage is 0 V. After the discharge is completed, short-circuit the battery, and repeat steps (3) and (4) in this way.

8. The method for using a non-chargeable thermal regeneration electrochemical cycle battery based on thermoelectric potential enhancement of thermosensitive crystals according to any one of claims 1 to 6, characterized in that: The specific steps are: S1 calibrates the electrode potentials of the positive electrolyte and the negative electrolyte at different temperatures, and draws a curve of the relationship between the electrode potential of the positive electrolyte and the temperature, and a curve of the relationship between the electrode potential of the negative electrolyte and the temperature, and the temperature at the intersection of the curve of the relationship between the electrode potential of the positive electrolyte and the temperature and the curve of the relationship between the electrode potential of the negative electrolyte and the temperature is recorded as the intermediate temperature T m ; S2 denotes the temperature at which the crystal precipitate in the positive electrode electrolyte or the negative electrode electrolyte is completely dissolved as the first temperature T1, and the temperature at which the crystal precipitate in the positive electrode electrolyte or the negative electrode electrolyte is precipitated as the second temperature T2; m , T1, T2 in degrees Celsius all satisfy: T1>T m , T2=2T m -T1, determining that the operating temperature range of the battery is from T2 to T1; S3: The difference between the slope of the positive electrode electrolyte electrode potential and temperature curve and the slope of the negative electrode electrolyte electrode potential and temperature curve is the battery thermoelectric potential; the battery is placed at the intermediate temperature T m When the battery thermoelectric potential is less than zero, the temperature is raised to a first temperature T1, at which time the battery voltage is negative, the positive and negative electrodes of the battery are switched, and then the battery is discharged until the battery voltage is 0V, and the battery is short-circuited after the discharge is completed; S4 then cools the battery to a second temperature T2 and discharges the battery again until the battery voltage is 0V. After the discharge is completed, the battery is short-circuited, and steps S3 and S4 are repeated.

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