CN111525179A - Preparation method of all-solid-state battery - Google Patents

Preparation method of all-solid-state battery Download PDF

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Publication number
CN111525179A
CN111525179A CN202010344918.3A CN202010344918A CN111525179A CN 111525179 A CN111525179 A CN 111525179A CN 202010344918 A CN202010344918 A CN 202010344918A CN 111525179 A CN111525179 A CN 111525179A
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electrolyte membrane
ground state
soluble
polymer
solid
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何特特
鞠博伟
曹景超
涂飞跃
覃事彪
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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 preparation method of an all-solid-state battery, which comprises the following steps: mixing the polycarbonate polymer, the matrix polymer, the soluble metal salt and the polar solvent, and uniformly stirring to obtain coating slurry; coating the coating slurry in a die to form a film, and drying to obtain a ground state electrolyte film; tightly packaging the ground state electrolyte membrane according to a cell structure of 'anode/ground state electrolyte membrane/cathode'; and (3) preserving the heat of the packaging material at 60-140 ℃ for 10-6000min to promote the conversion from the ground state electrolyte membrane to the self-wetting porous electrolyte membrane, thereby obtaining the all-solid-state battery. The invention utilizes the characteristic that the polycarbonate polymer can be gelled in situ, introduces the polymer with stable chemical properties as a self-supporting matrix, can form the self-wetting porous electrolyte membrane with micron or submicron micropore size in situ by blending, has no residual organic component loss, and conforms to the concept of environmental protection.

Description

Preparation method of all-solid-state battery
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a preparation method of an all-solid-state battery.
Background
The existing battery diaphragm manufacturing method comprises a wet process (thermally induced phase separation), a spray melting method, high-temperature stretching, an electron beam etching method and the like, and the preparation methods mainly aim at pore forming. The battery separator produced by the method is electrically insulating and has no ionic conductance. In actual work, the diaphragm is used for separating a positive electrode and a negative electrode after the battery is injected with liquid, so that short circuit is prevented. Therefore, the conventional separator needs to go through two processes from production to actual use: firstly, pore-forming and secondly liquid injection are carried out, and the process is complex.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings mentioned in the background technology, and provide a preparation method of an all-solid-state battery, wherein the preparation method can simultaneously realize pore forming and liquid injection of a diaphragm, and can effectively simplify the preparation process of the battery.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of an all-solid-state battery comprises the following steps:
(1) mixing the polycarbonate polymer, the matrix polymer, the soluble metal salt and the polar solvent, and fully stirring to obtain coating slurry;
(2) uniformly coating the coating slurry in a die to form a film, and drying to obtain a ground state electrolyte film;
(3) tightly packaging the ground state electrolyte membrane obtained in the step (2) according to a battery structure of 'anode/ground state electrolyte membrane/cathode';
(4) and (4) preserving the heat of the packaging material obtained in the step (3) for 10-6000min at the temperature of 60-140 ℃, and promoting the base state electrolyte membrane to be converted into the self-wetting porous electrolyte membrane, so that the all-solid-state battery is obtained. The temperature for heat preservation is not suitable to be too high, otherwise, the products of the pyrolysis of the polycarbonate polymer can generate obvious side reaction with the positive active material at high temperature, so that the positive material is corroded, the CEI is damaged, and the system is unstable.
In the preparation method, preferably, in the step (1), the content of the polycarbonate polymer is 5% -60%, the content of the matrix polymer is 20% -90%, and the content of the soluble metal salt is 2% -40%.
In the above preparation method, preferably, in the step (1), the viscosity of the coating slurry is 500-50000 mPas.
In the above production method, preferably, in the step (3), the ground state electrolyte membrane is in contact with the negative electrode.
In the above preparation method, preferably, in the step (3), the material used for the negative electrode is a strong reducing negative electrode material.
In the preparation method, preferably, the strong reducing negative electrode material includes one or more of metal lithium, sodium, potassium, calcium and indium.
In the above preparation method, preferably, in the step (3), the negative electrode material contains an alkaline substance having a pH of 10 or more, including but not limited to lithium hydroxide, sodium hydroxide, lithium oxide, sodium oxide, and the like.
In the above preparation method, preferably, in the step (1), the soluble metal salt is one or more of soluble lithium salt, soluble sodium salt, soluble magnesium salt, soluble aluminum salt, soluble potassium salt and soluble calcium salt.
In the preparation method, preferably, in the step (1), a proper amount of additives, such as nano silicon oxide, nano titanium oxide, PS, and the like, may also be added to the coating slurry.
The polycarbonate polymer is an environment-friendly polymer with poor stability, and when the polycarbonate polymer is contacted with a strong reducing substance or an alkaline substance, the polycarbonate polymer can be decomposed into lithium alkoxide with low polymerization degree and small molecular monomers, namely liquid electrolyte, such as PPC (polypropylene carbonate) and metallic lithium, and the liquid product PC (propylene carbonate) can be generated through decomposition in a high-temperature or alkaline environment. Based on the above, the invention introduces a polymer with stable chemical properties as a matrix to serve as a framework of a ground state film; the polycarbonate polymer is introduced as an auxiliary body, and can be decomposed after being contacted with metallic lithium or a strong reducing (or alkaline) negative electrode, a liquefied carbonate solvent can be generated, and finally a self-wetting porous electrolyte membrane is formed. The preparation process of the invention can be regarded as embedding the solidified liquid electrolyte into the polymer main matrix in a blending mode, then releasing the electrolyte in a liquid state after the battery is assembled, and realizing in-situ pore-forming while realizing self-wetting.
In the above preparation method, preferably, in the step (1), the structural formula of the polycarbonate-series polymer is as follows:
Figure BDA0002469719870000021
the values of a and b are integers within (1-10000);
R1is composed of
Figure BDA0002469719870000022
R2Is composed of
Figure BDA0002469719870000023
Wherein X is fluorine, phenyl, hydroxyl, alkyl, lithium sulfonate, sulfo or amino; m1+ n1 ═ 2; m2+ n2 ═ 2; m3+ n3 is 2.
In the above preparation method, preferably, in the step (1), the polycarbonate-series polymer is poly (ethylene carbonate), and the structural formula is as follows:
Figure BDA0002469719870000031
n is an integer of 2-10000.
In the above preparation method, preferably, the matrix polymer is not dissolved by the small molecule cyclic carbonate or alcohol solvent, and the matrix polymer includes, but is not limited to, polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyethylene oxide (PEO), Polyacrylonitrile (PAN), polyurethane, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polypropylene (PP), Polyethylene (PE), cellulose, Polyimide (PI), polyethylene terephthalate (PET), and more preferably, one or more of polyvinylidene fluoride (PVDF), polypropylene (PP), Polyethylene (PE), cellulose, and Polyimide (PI).
In the above preparation method, preferably, in step (1), the polar solvent includes one or more of acetonitrile, DMF, acetone, and NMP.
Compared with the prior art, the invention has the advantages that:
(1) the invention utilizes the characteristic that the polycarbonate polymer can be gelled in situ, introduces the polymer with stable chemical properties as a self-supporting matrix, can form the self-wetting porous electrolyte membrane with micron or submicron micropore size in situ by blending, has no residual organic component loss, and conforms to the concept of environmental protection.
(2) In the preparation process of the all-solid-state battery, a specific negative electrode material is introduced, and the heat preservation temperature is controlled to be 60-140 ℃ in the packaging process, so that the decomposition reaction of the polycarbonate polymer can be ensured, the in-situ pore-forming can be realized while the self-wetting is realized, and the phenomenon that the pyrolysis product of the polycarbonate polymer and the positive electrode active material generate obvious side reaction at an excessively high temperature to influence the instability of a battery system can be prevented.
(3) The invention fully combines the advantages of flexible production process of the solid-state battery and good electrochemical performance of the liquid electrolyte, and the performance of the solid-state battery is fully exerted.
(4) Compared with the existing solid-state battery technology, the all-solid-state battery can simultaneously realize the great improvement of the room-temperature conductivity and the interface wettability of the solid polymer electrolyte; compared with the liquid battery technology, the two processes of diaphragm pore-forming and liquid injection can be combined into one, and the battery manufacturing process is effectively simplified.
Drawings
Fig. 1 is a graph of efficiency/specific capacity of a solid-state battery in example 1 of the present invention.
Fig. 2 is an SEM photograph of the self-wetting porous membrane in the solid-state battery in example 1 of the present invention.
Fig. 3 is an SEM photograph at high magnification of the self-wetting porous membrane in the solid-state battery in example 1 of the present invention.
Fig. 4 is a charge-discharge current-voltage relationship diagram of the solid-state battery in the comparative example of the invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The raw materials used in the following examples and comparative examples are shown in Table 1.
TABLE 1 raw materials used in examples and comparative example 1
Figure BDA0002469719870000041
Example 1:
the preparation method of the all-solid-state battery comprises the following steps:
(1) weighing 2g of PVDF, 4g of PPC and 1.8g of LiTFSI, adding 12g of DMF, and stirring for 6h to obtain coating slurry (the viscosity is 5000mPa & s);
(2) the coating slurry was uniformly coated on an area of 200cm2Then the circular polytetrafluoroethylene die is moved into an oven to be fully dried and taken off to obtain a ground state electrolyte membrane;
(3) encapsulating the ground state electrolyte membrane in a structure of "commercialized NCM523 electrode sheet/ground state electrolyte membrane/metallic lithium", wherein the ground state electrolyte membrane is in contact with the negative electrode;
(4) and then preserving the temperature at 100 ℃ for 720min, and cooling to room temperature to obtain the all-solid-state battery taking the self-wetting porous membrane as the diaphragm.
The battery prepared in this example was subjected to a cycle performance test on a Land battery test system, and the charge-discharge regime was: the battery prepared by the technical scheme of the invention has good cycle performance, still has a specific discharge capacity of about 80mAh/g in 200 weeks, and has an average efficiency of about 99%. Therefore, the battery assembled by the preparation method can be normally charged and discharged, and the capacity exertion and the efficiency are close to those of a liquid battery.
An all-solid-state battery is prepared according to the preparation method of the embodiment 1, the battery is disassembled, the self-wetting porous membrane is taken out to test the conductivity of the self-wetting porous membrane and observe the morphology of the self-wetting porous membrane, as shown in fig. 2 and 3, the pore-forming of the scheme of the invention is successfully realized, the pore diameter is between 1 and 4 microns, and the distribution is relatively uniform.
The self-wetting porous membrane was assembled into a plugged cell of "stainless steel/solid electrolyte membrane/stainless steel" construction, and the impedance of the plugged cell was tested at an electrochemical workstation at a frequency range of 1Hz-1MHz, with the results shown in Table 2.
Example 2:
the preparation method of the all-solid-state battery comprises the following steps:
(1) 0.6g of nano titanium oxide was added to 16g of NMP to be ultrasonically dispersed, followed by 2g of PMMA, 6g of PEC and 1.5g of LiClO4Adding the mixture into the solution, fully dissolving, and stirring to obtain coating slurry;
(2) the coating slurry was uniformly coated on an area of 300cm2Then the circular polytetrafluoroethylene die is moved into an oven to be fully dried and taken off to obtain a ground state electrolyte membrane;
(3) packaging the ground state electrolyte membrane according to a structure of 'commercialized LFP electrode slice/ground state electrolyte membrane/metallic lithium', wherein the ground state electrolyte membrane is in contact with the negative electrode;
(4) and then preserving the heat at 100 ℃ for 1080min, and cooling to room temperature to obtain the all-solid-state battery taking the self-wetting porous membrane as the diaphragm.
The preparation method of example 3 is the same as that of example 1, except for the differences of the raw materials and the process parameters, and the raw materials and the process parameters in example 3 are shown in table 1.
Examples 4-6 were prepared in the same manner as example 2, except for the differences in the starting materials and process parameters, which are shown in Table 1 in examples 4-6.
The batteries prepared in examples 2 to 6 were disassembled, and the self-wetting porous membrane was taken out to test the conductivity of the electrolyte membrane of the self-wetting porous membrane in the same manner as in example 1, and the test results are shown in table 2. As can be seen from the results in table 2, the impedance of the self-wetting porous membrane is below 5 Ω, and the room-temperature ionic conductivity is in the mS level, which is close to or reaches the level of "liquid electrolyte + membrane" conductivity under the conventional "membrane-liquid injection" process.
TABLE 2
Figure BDA0002469719870000051
Figure BDA0002469719870000061
Comparative example:
the method for manufacturing the all-solid-state battery of the comparative example includes the steps of:
(1) weighing 2g of PVDF, 4g of PPC and 1.8g of LiTFSI, adding 12g of DMF, stirring for 6h, and blending to obtain coating slurry;
(2) coating the mixture in an area of 200cm2Uniformly spreading the circular polytetrafluoroethylene mold into a certain thickness, then transferring the circular polytetrafluoroethylene mold into an oven to be fully dried, and removing the circular polytetrafluoroethylene mold to obtain a final ground state film;
(3) packaging the obtained ground state film according to the structure of 'commercialized NCM523 electrode plate/solid electrolyte film/metallic lithium';
(4) and then preserving the temperature at 200 ℃ for 50min, and cooling to room temperature to obtain the battery with the self-wetting porous membrane as the separator.
The room temperature film resistance and the room temperature ionic conductivity of the battery of the comparative example were tested, and as shown in table 2, the room temperature film resistance and the room temperature ionic conductivity of the battery prepared by the comparative example also reach the levels equivalent to those of the technical solution of the present invention, but the open circuit voltage of the battery at 0% SOC is as high as 4.26V, and normal charging and discharging cannot be performed subsequently, that is, a battery with normal cycle cannot be obtained by the method (as shown in the charging and discharging current-voltage relationship diagram of fig. 4). The reason is presumed that substances such as pyrolysis products of PPC and PC may have a significant side reaction with the positive electrode active material at a high temperature of 200 ℃, so that the positive electrode material is corroded, CEI is destroyed, and the system is unstable; furthermore, PVDF is also thermally deformed and even melted at a high temperature of 200 ℃, and performance of battery performance is also affected.

Claims (10)

1. A preparation method of an all-solid-state battery is characterized by comprising the following steps:
(1) mixing the polycarbonate polymer, the matrix polymer, the soluble metal salt and the polar solvent, and uniformly stirring to obtain coating slurry;
(2) coating the coating slurry in a mold to form a film, and drying to obtain a ground state electrolyte film;
(3) tightly packaging the ground state electrolyte membrane obtained in the step (2) according to a battery structure of 'anode/ground state electrolyte membrane/cathode';
(4) and (4) preserving the heat of the packaging material obtained in the step (3) for 10-6000min at the temperature of 60-140 ℃, and promoting the base state electrolyte membrane to be converted into the self-wetting porous electrolyte membrane to obtain the all-solid-state battery.
2. The production method as claimed in claim 1, wherein in the step (1), the viscosity of the coating slurry is 500-50000 mPa-s.
3. The production method according to claim 1, wherein in the step (3), the ground state electrolyte membrane is in contact with a negative electrode.
4. The production method according to claim 1, wherein in the step (3), the material used for the negative electrode is a strongly reducing negative electrode material.
5. The preparation method according to claim 4, wherein the strong reducing negative electrode material comprises one or more of metal lithium, sodium, potassium, calcium and indium.
6. The method according to claim 1, wherein in the step (3), the negative electrode material contains an alkaline substance having a pH of 10 or more.
7. The method according to claim 1, wherein in the step (1), the soluble metal salt is one or more selected from the group consisting of a soluble lithium salt, a soluble sodium salt, a soluble magnesium salt, a soluble aluminum salt, a soluble potassium salt and a soluble calcium salt.
8. The method according to claim 1, wherein in the step (1), the polycarbonate-based polymer has a general structural formula as follows:
Figure FDA0002469719860000011
the values of a and b are integers within (1-10000);
R1is composed of
Figure FDA0002469719860000012
R2Is composed of
Figure FDA0002469719860000021
Wherein X is fluorine, phenyl, hydroxyl, alkyl, lithium sulfonate, sulfo or amino; m1+ n1 ═ 2; m2+ n2 ═ 2; m3+ n3 is 2.
9. The method according to claim 1, wherein in the step (1), the polycarbonate-series polymer is a poly (ethylene carbonate) having a structural formula as follows:
Figure FDA0002469719860000022
n is an integer of 2-10000.
10. The method according to claim 1, wherein in the step (1), the matrix polymer comprises one or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyethylene oxide (PEO), Polyacrylonitrile (PAN), polyurethane, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polypropylene (PP), Polyethylene (PE), cellulose, Polyimide (PI), and polyethylene terephthalate (PET).
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CN111900485A (en) * 2020-08-05 2020-11-06 中国科学院上海硅酸盐研究所 Slow-release modification method for solid electrolyte/metal lithium interface and solid lithium metal battery
CN113178617A (en) * 2021-04-19 2021-07-27 中国科学院化学研究所 Flame-retardant solid-liquid mixed solid electrolyte, preparation method thereof and lithium battery containing same
CN114512714A (en) * 2022-01-20 2022-05-17 贵阳学院 Composite polymer electrolyte material, preparation method thereof and lithium ion battery

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Publication number Priority date Publication date Assignee Title
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CN111900485B (en) * 2020-08-05 2022-03-04 中国科学院上海硅酸盐研究所 Slow-release modification method for solid electrolyte/metal lithium interface and solid lithium metal battery
CN113178617A (en) * 2021-04-19 2021-07-27 中国科学院化学研究所 Flame-retardant solid-liquid mixed solid electrolyte, preparation method thereof and lithium battery containing same
CN113178617B (en) * 2021-04-19 2023-01-31 中国科学院化学研究所 Flame-retardant solid-liquid mixed solid electrolyte, preparation method thereof and lithium battery containing same
CN114512714A (en) * 2022-01-20 2022-05-17 贵阳学院 Composite polymer electrolyte material, preparation method thereof and lithium ion battery

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