CN113972372A - Metal graphite medium-temperature energy storage battery and preparation method thereof - Google Patents

Metal graphite medium-temperature energy storage battery and preparation method thereof Download PDF

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Publication number
CN113972372A
CN113972372A CN202111131626.2A CN202111131626A CN113972372A CN 113972372 A CN113972372 A CN 113972372A CN 202111131626 A CN202111131626 A CN 202111131626A CN 113972372 A CN113972372 A CN 113972372A
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battery
energy storage
pole piece
additive
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宁晓辉
杨豪
张文龙
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Xian Jiaotong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a metal graphite medium-temperature energy storage battery and a preparation method thereof, and YCl is coated by a slurry coating method2the/C product, the binder, the conductive carbon black and the additive X are uniformly mixed and coated on a current collector, so that the preparation of the negative electrode material is quantitative and controllable; the additive X (X is Ni, Cu, Fe or Mn) is added into the negative electrode to form a complete and effective conductive network, so that the overall conductivity of the negative electrode material is improved. In addition, Y/YCl can be inhibited during the cell reaction by the synergistic effect between the additive X and the negative electrode metal Y2The volume change caused by particle growth in solid phase transformation obviously improves the defect of battery performance reduction caused by the volume change of a negative electrode and poor conductivity, greatly improves the utilization rate of battery materials and the capacity of a single battery, further reduces the production cost of the battery, and is a metal graphite batteryThe scale application of the method provides technical support.

Description

Metal graphite medium-temperature energy storage battery and preparation method thereof
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a preparation method for improving the performance of a metal graphite medium-temperature energy storage battery.
Background
Renewable energy sources such as solar energy, wind energy and the like and new energy automobiles are important ways and means for dealing with global energy crisis and relieving environmental pressure. However, the power generation by using new energy such as wind energy, solar energy and the like has randomness, volatility and anti-peak regulation characteristics, large-scale new energy power consumption still faces greater challenges, and the problem of wind abandonment and light abandonment is prominent, so that an energy storage technology with low cost and high safety is required as a support to realize convenient and reliable grid-connected power generation of the new energy.
The current common power grid energy storage technologies comprise water pumping energy storage, flywheel energy storage, compressed air energy storage and electrochemical energy storage, which have advantages and disadvantages respectively. Compared with a mechanical energy storage technology, the electrochemical energy storage technology has more advantages in the aspects of expandability, service life, flexibility and the like, occupies an increasingly important position in the development of new energy industry, and becomes the most main factor restricting the development of the whole industry. Energy storage technologies such as sodium-sulfur batteries, lead-acid batteries, lithium ion batteries and the like are all applied to the field of power grid energy storage. The sodium-sulfur battery has high theoretical energy density, high charge-discharge efficiency and long cycle life, but is operated at the temperature of 300-350 ℃, so that the durability and the sealing property of the battery material are important challenges; the lead-acid battery has low cost and can be produced in batch, but the energy density is low and the cycle life is short; the lithium ion battery has good energy efficiency, but the lithium ion battery is not easy to expand and has high price, so that the large-scale application of the lithium ion battery in power grid energy storage is limited.
In summary, there is no battery energy storage technology that can meet all the requirements of large-scale energy storage. Therefore, continuous optimization of existing energy storage technologies and development of novel electrochemical energy storage technologies are the research hotspots in the current energy storage field.
Disclosure of Invention
The invention provides a metal graphite medium-temperature energy storage battery and a preparation method thereof, and solves the problems of low utilization rate of a metal graphite battery cathode material, low single battery capacity, poor cycle stability and the like through the addition of an additive X.
In order to achieve the purpose, the invention provides a metal graphite medium-temperature energy storage battery, which comprises a positive pole piece, a negative pole and an electrolyte; the positive pole piece is made of graphite materials; the electrolyte is LiAlCl4、NaAlCl4And/or KAlCl4(ii) a The negative electrode comprises a negative electrode pole pieceThe pole piece is composed of YCl2YCl made of/C, conductive carbon black, binder and additive X2and/C, the mass ratio of the conductive carbon black to the binder is (5-7): 1-3):2, and the additive X is Ni, Cu, Fe or Mn.
Further, the mass of the additive X is 5-20% of the mass of the negative electrode active material.
Further, Y is a metal having higher electronegativity than Al.
Further, the binder is polyacrylic acid, polyimide or polyvinylidene fluoride.
Further, the graphite material includes graphite paper, graphene, carbon nanotubes or graphite intercalation compound.
A preparation method of the metal graphite medium-temperature energy storage battery comprises the following steps:
step 1, preparing a negative pole piece and a positive pole piece: subjecting the solid-phase YCl2Uniformly mixing the conductive agent, the adhesive, the liquid solvent, the conductive agent and the additive X to obtain slurry, uniformly coating the slurry on a negative current collector, and drying to obtain a negative pole piece; preparing a positive pole piece from a graphite material;
step 2, preparing electrolyte: taking NaAlCl4、LiAlCl4And KAlCl4As an electrolyte, one or more mixed salts of (a);
step 3, packaging the battery: and encapsulating the negative pole piece, the positive pole piece and the electrolyte in a battery shell.
Further, in step 1, YCl is immobilized2The preparation method comprises the following steps:
mixing YCl2Dehydrating and drying the powder to obtain anhydrous YCl2Powdering, drying the resultant anhydrous YCl2Fully mixing the powder and an inorganic carbon source, and then carrying out vacuum ball milling in a ball mill to obtain YCl with refined particles and uniform mixing2/C。
Furthermore, the used additive X is powdery, and the positive pole piece is made of flaky materials.
Compared with the prior art, the invention has at least the following beneficial technical effects:
1) the additive X provided by the invention can form a conductive network, improve the overall conductivity of the negative electrode material, and inhibit the deactivation of the active material caused by the volume change of the active material in the charging and discharging processes; meanwhile, through the synergistic effect of the additive X and the negative electrode metal Y, Y/YCl in the battery reaction process is inhibited2The volume change caused by particle growth in solid phase transformation improves the utilization rate of the metal graphite battery cathode and the capacity of the single battery, and provides technical support for large-scale production and industrial application of the metal graphite medium-temperature energy storage battery.
2) The additive X has wide source and is easy to prepare. The battery performance can be obviously improved by adding a small amount of additives, the capacity and the material utilization rate of the single battery are improved, and the production cost of the battery is further reduced.
Furthermore, the mass of the additive X is 5-20% of that of the negative active material, so that the capacity of the battery is not reduced and the increase of the production cost of the battery is avoided under the conditions of ensuring the establishment of a good conductive network, improving the conductivity of the negative active material and obviously improving the performance of the battery.
The preparation method of the negative electrode adopts the common slurry coating method for preparing the lithium ion pole piece to coat the active material YCl2And C, uniformly mixing the binder, the conductive carbon black, the liquid solvent and the additive, then coating the mixture on a negative current collector, and carrying out vacuum drying to obtain the battery pole piece with uniform thickness. The pole piece can operate at a medium temperature, and excellent multiplying power and cycle performance are obtained. Compared with the preparation of Y | YCl by HCl gas etching2The solid-phase composite electrode method and the slurry coating method can accurately control the content of active substances on the electrode plate, and the preparation method is simpler and more efficient.
The metal graphite medium-temperature energy storage battery has the advantages of low cost, long service life, excellent rate performance, no dendritic crystal, high safety and the like, and can be conveniently and quickly produced in an enlarged way through the design and preparation of a negative electrode material, so that the metal graphite medium-temperature energy storage battery becomes a battery technology which has a very promising prospect and is suitable for the commercial large-scale power grid energy storage market.
Drawings
FIG. 1 is a schematic diagram of the structure of a metal graphite medium-temperature battery and a composition diagram of a negative electrode plate after an additive X is added;
fig. 2 is a charge-discharge performance curve of the metal graphite battery using example 1 of the present invention;
fig. 3 is a charge-discharge performance curve of the metal graphite battery using example 2 of the present invention;
fig. 4 is a charge-discharge performance curve of the metal graphite battery using example 3 of the present invention;
fig. 5 is a charge-discharge performance curve of the metal graphite battery using example 4 of the present invention;
fig. 6 is a cycle capacity diagram of a metal graphite battery employing example 5 of the present invention;
in the drawings: 1-negative pole lead, 2-negative pole shell, 3-negative pole piece, 4-electrolyte, 5-positive pole piece, 6-positive pole shell, 7-positive pole lead, 8-additive X, 9-YCl2C particles, 10-negative current collector and 11-sealing washer;
the left side view in fig. 1 is a schematic structural diagram of a metal graphite medium-temperature battery; the right side of fig. 1 is a composition diagram of the negative electrode sheet after the additive X is added.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Referring to fig. 1, the metal graphite medium-temperature energy storage battery comprises a shell, a negative electrode, a sealing gasket, an electrolyte 4, a positive electrode plate 5, a negative electrode lead 1 and a positive electrode lead 7. Wherein, the shell includes negative pole shell 2 and positive casing 6, and the negative pole includes negative pole piece 3 and the negative current collector 10 that meets with negative pole piece 3, and negative lead 1 one end is connected with the negative pole, and the other end is worn out negative casing 2, and positive lead 7 one end is connected with positive pole piece 5, and the other end is worn out positive casing 6, places electrolyte 4 in the seal ring 11. The electrolyte is saturated MAlCl4M is Li, Na or K. The positive electrode is made of graphite materials, including graphite paper, graphene, carbon nanotubes or graphite intercalation compounds. The sealing washer is made of polytetrafluoroethylene material, the negative electrode shell and the positive electrode shell are extruded to the sealing washer by external force, the sealing washer deforms, and then the polytetrafluoroethylene sealing washer is heatedThermal expansion occurs to achieve the sealing effect.
Referring to fig. 1, a negative electrode sheet is shown in a composition diagram. The negative pole piece is prepared by coating slurry and adding active substance YCl2And uniformly mixing the/C particles 9, the binder, the conductive carbon black, the liquid solvent and the additive X8, then coating the mixture on a negative current collector, and carrying out vacuum drying to obtain the negative pole piece.
Wherein the binder is polyacrylic acid, polyimide or polyvinylidene fluoride; the liquid solvent is cyclohexanone, methyl ethyl ketone or N-methyl pyrrolidone; the conductive carbon black is Super P, Ketjen black or acetylene black; the negative current collector is a 0.03mm thick Al, Mo or Cu sheet.
1) Preparing a negative pole piece:
first, YCl is prepared2/C，YCl2The preparation method comprises the following steps:
YCl to be purchased2Dehydrating and drying the powder to obtain anhydrous YCl2Fully mixing the powder with an inorganic carbon source (Ketjen black, acetylene black or graphene), then carrying out vacuum ball milling in a ball mill, and obtaining YCl with the average particle size of 100nm, refined particles and uniform mixing after 6h2The product of the reaction/C.
Then the active substance YCl is added2And uniformly mixing the conductive carbon black, the adhesive, the conductive carbon black and the additive X to obtain slurry, uniformly coating the slurry on a negative current collector, and drying to obtain the negative pole piece.
Preferably, the additive X is Cu, Ni, Fe or Mn, and the content of the additive is 5% -20% of the content of the active substance in the negative pole piece. The additive content is too low, a good conductive network cannot be established, the conductivity of the negative active material is improved, and the battery performance is obviously improved; too high an additive content may reduce the active substance YCl2The content of the organic silicon compound reduces the capacity of the single battery and increases the production cost of the battery.
2) The preparation method of the molten salt electrolyte comprises the following steps:
99.9% high purity MCl and AlCl from Allatin3Weighing the medicines according to a molar ratio of 1:1, and fully mixing and heating the medicines to a temperature above a melting point to obtain the totalCrystal composition MALCl4I.e. MCl + AlCl3→MAlCl4. Wherein M is Li, Na or K. Respectively preparing LiAlCl by adopting the method4、NaAlCl4And KAlCl4Then, the electrolyte was obtained by mixing them in the proportions shown in examples 1 to 9.
Preferably, the material of the negative electrode case 3 and the positive electrode case 6 is 304 stainless steel, and 304 stainless steel has high strength and good corrosion resistance, and is suitable for being used as a high-temperature sealing material.
The working principle of the metal graphite medium-temperature energy storage battery is as follows:
in the fully discharged state: negative electrode is loaded with YCl2The active substance of/C, the positive pole piece is graphite material, the electrolyte is one or more mixed MAlCl4A molten salt electrolyte solution;
in the charging state: solid phase YCl2To obtain electrons, Y2+To Y metal, Cl-Entering into molten salt electrolyte to react with cation Na in molten salt+Bonding, YCl generation on the negative electrode side2-solid transition of Y; on the side of the positive electrode,
Figure BDA0003280662180000061
entering graphite layers from molten salt electrolyte to form an intercalation mixture; because one of the molten salt electrolytes with the lowest melting point is adopted, the battery operating temperature is 100-200 ℃, and the balance voltage is related to the selection of the cathode metal and is about 0.8-1.8V.
The negative reaction of the cell is:
YCl2+2e-+2M+→Y+2MCl
the positive electrode reaction is:
AlCl4 -+Cn→Cn[AlCl4]+e-
the total reaction formula of the battery is as follows:
Figure BDA0003280662180000062
in the formula, Cn represents multilayer graphite.
Example 1
A metal graphite medium-temperature energy storage battery comprises a shell, a negative electrode, a sealing gasket, an electrolyte, a positive electrode piece, a negative electrode lead 1 and a positive electrode lead 7. The shell comprises a negative electrode shell and a positive electrode shell, the negative electrode comprises a negative electrode pole piece 3 and a negative electrode current collector 10, and electrolyte is placed in the sealing washer. The preparation method comprises the following steps:
1) and preparing a negative pole piece. Weighing FeCl according to the mass ratio of 5:1:22Adding a certain amount of additive Fe into the mixture, uniformly mixing the mixture in NMP (N-methyl pyrrolidone) solvent, pulping, coating and drying to obtain a uniform pole piece, wherein the mass ratio of the additive Fe is 5% of the mass of a negative active substance, the negative active substance refers to all substances of the negative pole piece except a current collector, YCl2C, a binder, conductive carbon black and an additive; the preparation process of the negative pole piece is to prevent YCl2The oxidation and moisture absorption by air require operation under a protective atmosphere, such as argon or nitrogen.
2) And (4) preparing an electrolyte. The prepared molten salt LiAlCl is added4And KAlCl4Uniformly mixing the components according to a molar ratio of 0.6:0.4, heating the mixture to a temperature above a melting point, reacting and preserving heat for 24 hours, then grinding the molten salt electrolyte for later use after the electrolyte is cooled;
3) the positive pole piece is pre-cut by graphite paper with good conductivity;
4) and assembling the battery and testing the performance of the battery.
The assembling process comprises the following steps:
the method comprises the steps of placing an anode plate 5 in an anode shell 6, enabling a first end of a sealing washer to be in contact with the anode plate 5, placing an electrolyte 4 in the sealing washer, placing a cathode plate 3 at a second end of the sealing washer, placing a cathode shell 2 outside the cathode plate 3, extruding the cathode shell 2 and the anode shell 6 simultaneously, enabling the sealing washer to be extruded and the sealing washer to deform, then enabling a polytetrafluoroethylene sealing washer to generate thermal expansion to achieve a sealing effect in the temperature rising process, and completing battery assembly.
The charge and discharge performance curve is shown in fig. 2, and it can be seen from fig. 2 that: the battery normally runs, the charging and discharging process is stable, and the short circuit condition does not occur; the charging voltage has three platforms, 1.25-1.3V, 1.35-1.4V and 1.5-1.6V respectively, and the discharging platform is 1.4-1.35V and 1.15-0.9V; the average capacity of the single battery is 260mAh/g, the material utilization rate reaches 65%, the coulombic efficiency is 95%, and the energy efficiency is 70%.
Example 2
A metal graphite medium-temperature energy storage battery is specifically prepared by the following steps:
1) and preparing a negative pole piece. Weighing FeCl according to the mass ratio of 5:2:22Adding a certain amount of additive Cu into the mixture, uniformly mixing the mixture in an NMP (N-methyl pyrrolidone) solvent, and then pulping, coating and drying to obtain a uniform pole piece, wherein the mass ratio of the additive Cu is 8% of the mass of the negative active material;
2) and (4) preparing an electrolyte. The prepared molten salt LiAlCl is added4And KAlCl4Uniformly mixing the components according to a molar ratio of 0.6:0.4, heating the mixture to a temperature above a melting point, reacting and preserving heat for 24 hours, then grinding the molten salt electrolyte for later use after the electrolyte is cooled;
3) graphene for the positive electrode plate;
4) and assembling the battery and testing the performance of the battery.
The charge and discharge performance curves are shown in fig. 3, and it can be seen that: the charging and discharging of the battery are single platforms, the charging voltage platform is 1.6-1.8V, and the discharging platform is 1.2-0.9V; the average capacity of the single battery is 90mAh/g, the material utilization rate reaches 20%, the coulombic efficiency is 99%, and the energy efficiency is 70%.
Example 3
The preparation method of the metal graphite medium-temperature energy storage battery comprises the following steps:
1) and preparing a negative pole piece. Weighing FeCl according to the mass ratio of 5:3:22Adding a certain amount of additive Ni into the mixture, uniformly mixing the mixture in an NMP (N-methyl pyrrolidone) solvent, and then pulping, coating and drying to obtain a uniform pole piece, wherein the mass ratio of the additive Ni to the negative active material is 10%;
2) and (4) preparing an electrolyte. The prepared molten salt LiAlCl is added4And KAlCl4Uniformly mixing the components according to a molar ratio of 0.7:0.3, heating the mixture to a temperature above a melting point, reacting and preserving heat for 24 hours, then grinding the molten salt electrolyte for later use after the electrolyte is cooled;
3) the positive pole piece is pre-cut by graphite paper with good conductivity;
4) and assembling the battery and testing the performance of the battery.
The charge and discharge performance curves are shown in fig. 4, as shown in the figure: the battery normally operates, and the charging and discharging process is stable; the charging voltage of the single platform is 1.2-1.4V, and the discharging platform is 1.25-0.9V; the average capacity of the single battery is 280mAh/g, the material utilization rate reaches 70%, the coulombic efficiency is 96%, and the energy efficiency is 75%.
Example 4
A metal graphite medium-temperature energy storage battery is specifically prepared by the following steps:
1) and preparing a negative pole piece. Weighing FeCl according to the mass ratio of 6:1:22Adding a certain amount of additive Mn into the product/C, PVDF (polyvinylidene fluoride) and acetylene black, uniformly mixing the additive Mn in an NMP (N-methyl pyrrolidone) solvent, and then pulping, coating and drying to obtain a uniform pole piece, wherein the mass ratio of the additive Mn is 12% of the mass of the negative active material;
2) and (4) preparing an electrolyte. The prepared molten salt LiAlCl is added4And KAlCl4Uniformly mixing the components according to a molar ratio of 0.7:0.3, heating the mixture to a temperature above a melting point, reacting and preserving heat for 24 hours, then grinding the molten salt electrolyte for later use after the electrolyte is cooled;
3) carbon nanotubes for the positive electrode sheet;
4) and assembling the battery and testing the performance of the battery.
The charge and discharge performance curve chart is shown in fig. 5, the battery normally operates, the charge and discharge process is stable, and the short circuit condition does not occur; the charging voltage platform is 1.2-1.35V, and the discharging platform is 1.3-1V; the discharge capacity of the single battery is 340mAh/g, the material utilization rate reaches 80%, the coulombic efficiency is 90%, and the energy efficiency is 70%.
Example 5
A metal graphite medium-temperature energy storage battery is specifically prepared by the following steps:
1) and preparing a negative pole piece. Weighing NiCl according to the mass ratio of 6:2:22Adding a certain amount of additive Fe into the mixture, uniformly mixing the mixture in an NMP (N-methyl pyrrolidone) solvent, and then pulping, coating and drying to obtain a uniform pole piece, wherein the mass ratio of the additive Fe is 15% of the mass of the negative active material;
2) and (4) preparing an electrolyte. The prepared molten salt LiAlCl is added4And KAlCl4Uniformly mixing the components according to a molar ratio of 0.7:0.3, heating the mixture to a temperature above a melting point, reacting and preserving heat for 24 hours, then grinding the molten salt electrolyte for later use after the electrolyte is cooled;
3) the positive pole piece is pre-cut by graphite paper with good conductivity;
4) and assembling the battery and testing the performance of the battery.
The cycle capacity curve chart is shown in fig. 6, the battery normally operates, the charging and discharging process is stable, the battery stably operates for 100 cycles, the average capacity of the single battery is 330mAh/g, the material utilization rate is 80%, the coulombic efficiency is 99%, and the energy efficiency is 75%.
Example 6
A metal graphite medium-temperature energy storage battery comprises a shell, a negative electrode, a gasket, an electrolyte and a positive electrode. The left and right shells are positive and negative leads, and the electrolyte is placed in the sealing washer, and the preparation method comprises the following steps:
1) and preparing a negative pole piece. Weighing NiCl according to the mass ratio of 6:3:22The method comprises the following steps of (1) adding a certain amount of additive Ni into a/C product, PVDF (polyvinylidene fluoride) and acetylene black, uniformly mixing the additive Ni in an NMP (N-methyl pyrrolidone) solvent, and then pulping, coating and drying to obtain a uniform pole piece, wherein the mass ratio of the additive Ni is 20% of the mass of a negative active substance;
2) and (4) preparing an electrolyte. The prepared molten salt LiAlCl is added4And KAlCl4Uniformly mixing according to the molar ratio of 0.7:0.3, heating to a temperature above the melting point, reacting, keeping the temperature for 24 hours, cooling the electrolyte, and electrolyzing the molten saltGrinding the decomposition material and bottling for later use;
3) a graphite interlayer compound for the positive pole piece;
4) and assembling the battery and testing the performance of the battery.
Example 7
A metal graphite medium-temperature energy storage battery is specifically prepared by the following steps:
1) and preparing a negative pole piece. Weighing NiCl according to the mass ratio of 7:1:22The method comprises the following steps of (1) adding a certain amount of additive Cu into a/C product, PVDF (polyvinylidene fluoride) and acetylene black, uniformly mixing the additive Cu in an NMP (N-methyl pyrrolidone) solvent, and then pulping, coating and drying to obtain a uniform pole piece, wherein the mass ratio of the additive Cu is 5% of the mass of a negative active substance;
2) and (4) preparing an electrolyte. The prepared molten salt LiAlCl is added4And KAlCl4Uniformly mixing the components according to a molar ratio of 0.8:0.2, heating the mixture to a temperature above a melting point, reacting and preserving heat for 24 hours, then grinding the molten salt electrolyte for later use after the electrolyte is cooled;
3) the positive pole piece is pre-cut by graphite paper with good conductivity;
4) and assembling the battery and testing the performance of the battery.
Example 8
A metal graphite medium-temperature energy storage battery is specifically prepared by the following steps:
1) and preparing a negative pole piece. Weighing ZnCl according to the mass ratio of 7:2:22Adding a certain amount of additive Mn into the product/C, PVDF (polyvinylidene fluoride) and acetylene black, uniformly mixing the additive Mn in an NMP (N-methyl pyrrolidone) solvent, and then pulping, coating and drying to obtain a uniform pole piece, wherein the mass ratio of the additive Mn is 5% of the mass of the negative active material;
2) and (4) preparing an electrolyte. The prepared molten salt LiAlCl is added4And KAlCl4Uniformly mixing the components according to a molar ratio of 0.8:0.2, heating the mixture to a temperature above a melting point, reacting and preserving heat for 24 hours, then grinding the molten salt electrolyte for later use after the electrolyte is cooled;
3) the positive pole piece is pre-cut by graphite paper with good conductivity;
4) and assembling the battery and testing the performance of the battery.
Example 9
A metal graphite medium-temperature energy storage battery is specifically prepared by the following steps:
1) and preparing a negative pole piece. Weighing ZnCl according to the mass ratio of 7:3:22Adding a certain amount of additive Fe into the mixture, uniformly mixing the mixture in an NMP (N-methyl pyrrolidone) solvent, and then pulping, coating and drying to obtain a uniform pole piece, wherein the mass ratio of the additive Fe is 20% of the mass of the negative active material; the preparation process of the cathode material is to prevent YCl2The oxidation and moisture absorption by air require operation under a protective atmosphere, such as argon or nitrogen.
2) And (4) preparing an electrolyte. The prepared molten salt LiAlCl is added4And KAlCl4Uniformly mixing the components according to a molar ratio of 0.6:0.4, heating the mixture to a temperature above a melting point, reacting and preserving heat for 24 hours, then grinding the molten salt electrolyte for later use after the electrolyte is cooled;
3) the positive pole piece is pre-cut by graphite paper with good conductivity;
4) and assembling the battery and testing the performance of the battery.
The assembling process comprises the following steps:
the method comprises the steps of placing an anode piece in an anode shell, enabling a first end of a sealing washer to be in contact with the anode piece, placing electrolyte in the sealing washer, placing a cathode piece at a second end of the sealing washer, placing a cathode shell outside the cathode piece, simultaneously extruding the cathode shell and the anode shell, enabling the sealing washer to be extruded and the sealing washer to deform, then enabling a polytetrafluoroethylene sealing washer to generate thermal expansion to achieve a sealing effect in a temperature rising process, and completing battery assembly.
The foregoing examples are provided for the purpose of clarity only and are not intended to be limiting. It should be noted that similar alterations and modifications of the present invention based on the principles described herein will occur to those skilled in the art, and it is not intended to list all such embodiments, so that obvious modifications and variations of this invention are possible within the scope of the present invention.

Claims (8)

1. A metal graphite medium-temperature energy storage battery is characterized by comprising a positive pole piece (5), a negative pole and an electrolyte (3); the positive pole piece (5) is made of graphite materials; the electrolyte (4) is LiAlCl4、NaAlCl4And/or KAlCl4(ii) a The negative electrode comprises a negative electrode plate (3) consisting of YCl2YCl made of/C, conductive carbon black, binder and additive X2and/C, the mass ratio of the conductive carbon black to the binder is (5-7): 1-3):2, and the additive X is Ni, Cu, Fe or Mn.
2. The metal graphite medium-temperature energy storage battery as claimed in claim 1, wherein the mass of the additive X is 5-20% of the mass of the negative active material.
3. The metal graphite medium-temperature energy storage battery as claimed in claim 1, wherein Y is a metal with electronegativity higher than Al.
4. The metal graphite medium-temperature energy storage battery as claimed in claim 1, wherein the binder is polyacrylic acid, polyimide or polyvinylidene fluoride.
5. The metal graphite medium-temperature energy storage battery as claimed in claim 1, wherein the graphite material comprises graphite paper, graphene, carbon nanotubes or graphite intercalation compound.
6. A method for preparing a metal graphite medium-temperature energy storage battery in accordance with claim 1, characterized by comprising the following steps:
step 1, preparing a negative pole piece (3) and a positive pole piece (5): subjecting the solid-phase YCl2Uniformly mixing the/C, the binder, the liquid solvent, the conductive agent and the additive X to obtain slurry, uniformly coating the slurry on a negative current collector (10), and drying to obtain a negative pole piece (3); using graphite-like materialsManufacturing a positive pole piece (5);
step 2, preparing an electrolyte (4): taking NaAlCl4、LiAlCl4And KAlCl4As an electrolyte, one or more mixed salts of (a);
step 3, packaging the battery: and the negative pole piece (3), the positive pole piece (5) and the electrolyte (4) are packaged in a battery shell.
7. The method for preparing metal graphite medium-temperature energy storage battery according to claim 6, characterized in that in step 1, solid-phase YCl2The preparation method comprises the following steps:
mixing YCl2Dehydrating and drying the powder to obtain anhydrous YCl2Powdering, drying the resultant anhydrous YCl2Fully mixing the powder and an inorganic carbon source, and then carrying out vacuum ball milling in a ball mill to obtain YCl with refined particles and uniform mixing2/C。
8. The method for preparing a metal graphite medium-temperature energy storage battery according to claim 6, characterized in that the used additive X is in a powder form, and the positive electrode piece is made of a sheet material.
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