CN108598557B - All-solid-state battery integrated module and all-solid-state battery comprising same - Google Patents

All-solid-state battery integrated module and all-solid-state battery comprising same Download PDF

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CN108598557B
CN108598557B CN201810495324.5A CN201810495324A CN108598557B CN 108598557 B CN108598557 B CN 108598557B CN 201810495324 A CN201810495324 A CN 201810495324A CN 108598557 B CN108598557 B CN 108598557B
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CN108598557A (en
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许晓雄
崔言明
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Zhejiang Funlithium New Energy Tech 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
    • 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

Abstract

The invention relates to the technical field of all-solid-state batteries, and mainly discloses an all-solid-state battery integrated module and an all-solid-state battery comprising the same, which are beneficial to improving the rapid assembly of the all-solid-state battery integrated module and a traditional counter electrode on one hand, and reduce the influence of interface impedance on the all-solid-state battery on the other hand because the number of interfaces of a battery core assembled by the all-solid-state battery integrated module is small and the thickness of a solid electrolyte is small. Moreover, the all-solid-state battery comprising the all-solid-state battery integrated module has higher electrical property and longer service life, thereby being suitable for popularization and use.

Description

All-solid-state battery integrated module and all-solid-state battery comprising same
Technical Field
The invention relates to the technical field of all-solid-state batteries, in particular to an all-solid-state battery integrated module and an all-solid-state battery comprising the module.
Background
In recent years, the global new energy automobile industry has explosively increased, the explosive development of electric automobiles is benefited, the demand of power batteries is rapidly increased, and the market space in the future is huge by combining 3C digital batteries and energy storage batteries. Solid-state batteries, which employ solid electrolytes instead of conventional organic liquid electrolytes, have been recognized as a way to prepare next-generation battery technologies. Compared with the traditional liquid battery, the battery is not easy to burn and explode, has better high-temperature performance, no flatulence and electrolyte leakage, and improves the safety performance. Therefore, the solid-state battery becomes the ultimate target of the battery, and is more in line with the requirements of future development in the fields of electric automobiles and large-scale energy storage.
The development and industrialization of solid-state batteries continue to increase the temperature, however, the battery core structure in the conventional solid-state batteries is sequentially overlapped to form a positive current collector, a positive material, a solid electrolyte, a negative material and a negative current collector. Thus, each layer of material needs to be separately produced and then bonded together, so that the interfaces between the materials are relatively obvious, and the interface impedance is relatively large.
Disclosure of Invention
The invention aims to provide an all-solid-state battery integrated module, which has much fewer interface gaps compared with the traditional battery core, so that the interface impedance is relatively small, and the overall electrical property of the manufactured all-solid-state battery is relatively high.
The above object of the present invention is achieved by the following technical solutions: an all-solid-state battery integrated module sequentially comprises a solid electrolyte, an electrode, a current collector, an electrode and a solid electrolyte, wherein the solid electrolyte and the electrode which are positioned on the same side of the current collector are integrally solidified into the integrated module.
By adopting the technical scheme, the solid electrolyte, the electrode, the current collector, the electrode and the solid electrolyte are integrally solidified. Therefore, it can be fabricated into a battery cell by simply attaching a conventional counter electrode. This not only reduces the interface, but also makes assembly much more convenient.
Preferably, the thickness of the solid electrolyte is 5-10 μm.
By adopting the technical scheme, as the solid electrolyte is generally required to be torn off for reassembly after being dried and solidified, the thickness of the solid electrolyte is required to be more than 50 μm in order to avoid the breakage of the solid electrolyte in the next process, so that the internal resistance of the electrode is increased. The solid electrolyte and the electrode are integrated, and the electrode is directly bonded on the current collector, so that the solid electrolyte does not need to be peeled off separately. Thus, the thickness of the solid electrolyte can be 5-10 μm. And the internal resistance of the whole battery core is reduced by 2-4 times under the thickness of the solid electrolyte. Furthermore, this also corresponds to the elimination of a portion of the interface problems between materials during cycling.
Preferably, the electrode comprises, by mass, 1-2 parts of carbon black, 7-9 parts of an electrode active material, 0.2-2 parts of an alkali metal salt and 1-5 parts of a polymer matrix; the solid electrolyte comprises 0.2-2 parts of alkali metal salt and 1-5 parts of polymer matrix by mass.
Preferably, the electrode active material may be any one of a positive electrode active material and a negative electrode active material, the positive electrode active material may be one of a lithium ion electrode material and a sodium ion electrode material, and the negative electrode active material may be any one of a metal lithium electrode, a double-sided graphite-based electrode, a double-sided silicon-carbon composite electrode, a metal sodium electrode, and a double-sided hard carbon electrode.
Preferably, the lithium ion electrode material may be any one of LFP, NCA, NCM, and lithium-rich.
Preferably, the sodium ion electrode material may be NaxMO2And NaxM(CN)6And M may be Ni, Mn, Fe, Co andany one of Cu.
Preferably, the polymer matrix can be any one or a mixture of several of polyoxyethylene, polycarbonate, polysiloxane and polymer lithium single-ion conductors.
Preferably, the alkali metal salt may be any one of a lithium salt and a sodium salt.
Preferably, the lithium salt may be LiN (SO)2CF3)2、LiClO4、LiSO2CF3And LiB (C)2O4)2Any one or a mixture of several of the above, and the sodium salt can be NaN (SO)2CF3)2、NaClO4、NaSO2CF3And NaB (C)2O4)2The anhydrous solvent can be any one or a mixture of more of acetonitrile, tetrahydrofuran, glycol dimethyl ether and N-methylpyrrolidone.
An all-solid-state battery comprises the above all-solid-state battery integrated module.
The all-solid-state battery is convenient to produce, has small internal resistance, and can still maintain large capacitance after being circulated for many times. And, the energy density of the whole all-solid-state battery is also relatively high.
In conclusion, the invention has the following beneficial effects:
1. the all-solid-state battery integrated module has fewer interfaces, so that the influence of interface impedance on the electrical property of the all-solid-state battery is weakened;
2. the thickness of the solid electrolyte can be thinner, so that the internal resistance of the battery core is reduced, and the integral electrical property of the battery is improved;
3. the all-solid-state battery integrated module is easy to pair with the traditional counter electrode, so that the production efficiency is improved, and the waste of resources can be reduced.
Drawings
Fig. 1 is a schematic structural view of an all-solid-state battery integrated module;
fig. 2 is a flow chart of the preparation of an all-solid-state battery integration module;
fig. 3 is a partial structural view of a battery cell;
fig. 4 is a schematic structural view of an all-solid battery including stacked battery cells;
fig. 5 is a schematic view of the structure of an all-solid-state battery including a wound battery cell.
In the figure, 1, a core; 11. an all-solid-state battery integration module; 111. an integration module; 112. a current collector; 12. a counter electrode; 2. an aluminum-plastic film; 3a, a positive terminal I; 3b, a negative electrode end I; 4. a housing; 5a, a second positive terminal; 5b and a second negative electrode terminal.
Detailed Description
The structure of the all-solid-state battery integrated module will be described in further detail with reference to fig. 1.
An all-solid-state battery integrated module sequentially comprises a solid electrolyte, an electrode, a current collector, an electrode and a solid electrolyte, wherein the solid electrolyte and the electrode are integrally solidified to form the integrated module 111, and an interface between the solid electrolyte and the electrode is fuzzy. Furthermore, the interface of the completed all-solid-state battery integrated module 11 exists only between the integrated module 111 and the current collector 112, so that the number of interfaces is relatively reduced compared to that of the conventional battery cell. So that the interface resistance is also reduced somewhat.
Meanwhile, after the solid electrolyte and the electrodes are integrated, the solid electrolyte can be made thinner, so that the material cost is reduced. Here, the thickness of the solid electrolyte is 5 to 10 μm.
Here, the internal resistance values of all-solid-state battery integrated modules having different thicknesses of solid electrolytes were measured, and the results are shown in the following table:
Figure BDA0001669002760000041
as is clear from the above table, when the thickness of the solid electrolyte is 10 μm or less, the internal resistance of the all-solid battery integrated module is significantly reduced, whereas when the thickness of the solid electrolyte is less than 5 μm, the processing cost is high due to the limitation of the technical level.
In addition, the all-solid-state battery integrated module can be combined with a traditional counter electrode for use, so that the traditional process is compatible, the preparation process is greatly simplified, the preparation efficiency of the all-solid-state battery is improved, the preparation cost is reduced, and the commercial development of the all-solid-state battery is expected to be promoted. And moreover, the electric energy conversion rate, the energy density and other electric properties of the battery are further improved.
The invention is described in further detail below with reference to the accompanying figure 2
The first embodiment is as follows:
a preparation method of an all-solid-state battery integrated module comprises the following steps:
the method comprises the following steps: in the case of dry gas, 8 parts of LFP, 1.5 parts of carbon black, 1.1 parts of LiB (C)2O4)2Adding 3 parts of polyoxyethylene group into acetonitrile, uniformly stirring to obtain a first slurry, and adjusting the acetonitrile content to a solid content of 75 vol%;
step two: in the case of dry gas, 3 parts of polyoxyethylene group and 1.1 parts of LiB (C)2O4)2Adding the mixture into acetonitrile, continuously stirring the mixture evenly to obtain a second slurry, and adjusting the acetonitrile content until the solid content is 45 vol%; step three: the first sizing agent corresponds to the front roller group, and the second sizing agent corresponds to the rear roller group;
step four: coating the first slurry on two sides of the current collector by the front roller group, wherein the coating thickness of the first slurry is 70 micrometers, coating the second slurry on the surface of the first slurry on two sides of the current collector by the rear roller group, wherein the coating thickness of the second slurry is 95 micrometers, and thus obtaining the prefabricated module
Step five: drying the prefabricated module at the synchronous temperature of 90 ℃ for 6 hours, and then synchronously rolling to obtain an all-solid-state battery integrated module with a sheet-shaped structure of solid electrolyte/electrode/current collector/electrode/solid electrolyte;
here, 50 μm lithium metal was used as a negative electrode, and the negative electrode was spread flat with the above-described all-solid-state battery integrated module, and wound to obtain an all-solid-state battery cell, and the thickness of the solid electrolyte after drying was about 7 μm.
Example two:
a preparation method of an all-solid-state battery integrated module comprises the following steps:
the method comprises the following steps: in the case of dry gas, 9 parts of NCA, 2 parts of carbon black, 2 parts of LiN (SO)2CF3)2Adding 5 parts of polycarbonate group into tetrahydrofuran, uniformly stirring to obtain a first slurry, and adjusting the content of the tetrahydrofuran to 90 vol% of solid content;
step two: in the case of a dry gas, 5 parts of polycarbonate base and 2 parts of LiN (SO)2CF3)2Adding the mixture into tetrahydrofuran, continuously stirring the mixture evenly to obtain a second slurry, and adjusting the content of the tetrahydrofuran until the solid content is 60 vol%;
step three: the first sizing agent corresponds to the front roller group, and the second sizing agent corresponds to the rear roller group;
step four: coating the first slurry on two sides of the current collector by the aid of the front roller group, wherein the coating thickness of the first slurry is 50 micrometers, coating the second slurry on the surface of the first slurry on two sides of the current collector by the aid of the rear roller group, and the coating thickness of the second slurry is 80 micrometers, so that a prefabricated module is obtained;
step five: drying the prefabricated module at the temperature of 100 ℃ for 8 hours synchronously, and then synchronously rolling to obtain an all-solid-state battery integrated module with a sheet-shaped structure of solid electrolyte/electrode/current collector/electrode/solid electrolyte;
here, 9 parts of graphite, 2 parts of carbon black, 2 parts of LiN (SO)2CF3)2And 5 parts of polycarbonate group are added into tetrahydrofuran to be mixed uniformly, the mixture is coated on copper foil, and the mixture is paved with the all-solid-state battery integrated module, and the all-solid-state battery cell is obtained through repeated lamination. Here, the thickness of the solid electrolyte after drying is about 10 μm.
Example three:
a preparation method of an all-solid-state battery integrated module comprises the following steps:
the method comprises the following steps: in the case of dry gas, 7 parts of NCM, 1 part of carbon black, 0.2 part of LiClO4Adding 1 part of polysiloxane into ethylene glycol dimethyl ether, uniformly stirring to obtain a first slurry, and adjusting the content of the ethylene glycol dimethyl ether to a solid content of 60 vol%;
step two: in the case of dry gas, 1 part of polysiloxane base and 0.2 part of LiClO4Adding the mixture into ethylene glycol dimethyl ether, continuously stirring the mixture evenly to obtain slurry II, and adjusting the content of the ethylene glycol dimethyl ether to the solid content of 30 vol%;
step three: the first sizing agent corresponds to the front roller group, and the second sizing agent corresponds to the rear roller group;
step four: coating the first slurry on two sides of the current collector by the aid of the front roller group, wherein the coating thickness of the first slurry is 70 micrometers, coating the second slurry on the surface of the first slurry on two sides of the current collector by the aid of the rear roller group, and the coating thickness of the second slurry is 90 micrometers, so that a prefabricated module is obtained;
step five: drying the prefabricated module at the temperature of 80 ℃ for 1h synchronously, and then synchronously rolling to obtain an all-solid-state battery integrated module with a sheet structure of solid electrolyte/electrode/current collector/electrode/solid electrolyte;
here, 7 parts of graphite, 1 part of carbon black, 0.2 part of LiClO4And adding 1 part of polycarbonate into ethylene glycol dimethyl ether, uniformly mixing, coating the mixture on copper foil, paving the copper foil and the all-solid-state battery integrated module, and winding to obtain the all-solid-state battery cell. Here, the thickness of the solid electrolyte after drying was about 5 μm, and the inert gas was mainly argon gas.
Example four:
a preparation method of an all-solid-state battery integrated module comprises the following steps:
the method comprises the following steps: in the case of dry gas, 7 parts of lithium-rich, 1.5 parts of carbon black, 2 parts of LiSO2CF3Adding 5 parts of polymer lithium single-ion conductor into N-methyl pyrrolidone, uniformly stirring to obtain a first slurry, and adjusting the content of the N-methyl pyrrolidone to 60 vol% of solid content;
step two: in the case of dry gas, 5 parts of polymeric lithium single-ion conductor and 0.2 part of LiSO2CF3Adding to N-methylpyrroleIn the alkanone, continuously stirring uniformly to obtain a second slurry, and adjusting the content of the N-methyl pyrrolidone to 60 vol% of solid content;
step three: the first sizing agent corresponds to the front roller group, and the second sizing agent corresponds to the rear roller group;
step four: coating the first slurry on two sides of the current collector by the aid of the front roller group, wherein the coating thickness of the first slurry is 50 micrometers, coating the second slurry on the surface of the first slurry on two sides of the current collector by the aid of the rear roller group, and the coating thickness of the second slurry is 25 micrometers, so that a prefabricated module is obtained;
step five: drying the prefabricated module at the temperature of 80 ℃ for 6 hours synchronously, and then synchronously rolling to obtain an all-solid-state battery integrated module with a sheet-shaped structure of solid electrolyte/electrode/current collector/electrode/solid electrolyte;
here, 7 parts of graphite, 1.5 parts of carbon black, 2 parts of LiSO2CF3And adding 1 part of polymer lithium single-ion conductor into N-methyl pyrrolidone, uniformly mixing, coating the mixture on copper foil, paving the copper foil and the all-solid-state battery integrated module, and repeatedly laminating to obtain an all-solid-state battery cell. Here, the thickness of the solid electrolyte after drying was about 7 μm.
Example five:
a preparation method of an all-solid-state battery integrated module comprises the following steps:
the method comprises the following steps: in the case of dry gas, 9 parts of graphite, 1 part of carbon black, 1.1 parts of LiN (SO)2CF3)20.9 parts of LiClO4Adding 3 parts of polycarbonate into acetonitrile, uniformly stirring to obtain a first slurry, and adjusting the acetonitrile content to a solid content of 90 vol%;
step two: in the case of a dry gas, 3 parts of polycarbonate base, 1.1 parts of LiN (SO)2CF3)2And 0.9 parts LiClO4Adding the mixture into acetonitrile, continuously stirring the mixture evenly to obtain a second slurry, and adjusting the acetonitrile content until the solid content is 45 vol%;
step three: the first sizing agent corresponds to the front roller group, and the second sizing agent corresponds to the rear roller group;
step four: coating the first slurry on two sides of the current collector by the aid of the front roller group, wherein the coating thickness of the first slurry is 90 micrometers, coating the second slurry on the surface of the first slurry on two sides of the current collector by the aid of the rear roller group, and the coating thickness of the second slurry is 30 micrometers, so that a prefabricated module is obtained;
step five: drying the prefabricated module at the temperature of 80 ℃ for 6 hours synchronously, and then synchronously rolling to obtain an all-solid-state battery integrated module with a sheet-shaped structure of solid electrolyte/electrode/current collector/electrode/solid electrolyte;
here, 7 parts of a double-sided LFP, 1 part of carbon black, 1.1 parts of LiN (SO)2CF3)20.9 parts of LiClO4And 3 parts of polycarbonate group are added into acetonitrile to be mixed uniformly, the mixture is coated on copper foil, and the copper foil and the all-solid-state battery integrated module are paved and wound to obtain an all-solid-state battery cell. Here, the thickness of the solid electrolyte after drying is about 10 μm, and the inert gas is neon.
Example six:
a preparation method of an all-solid-state battery integrated module comprises the following steps:
the method comprises the following steps: in the case of dry gas, 8 parts of silicon carbon material, 1.5 parts of carbon black, 0.6 part of LiSO2CF30.5 part of LiB (C)2O4)2Adding 2 parts of polyoxyethylene and 2 parts of polysiloxane into a mixed solution (volume ratio of 1: 1) of acetonitrile and N-methyl pyrrolidone, uniformly stirring to obtain a slurry I, and adjusting the content of the mixed solution (volume ratio of 1: 1) of acetonitrile and N-methyl pyrrolidone to 75 vol% of solid content;
step two: in the case of dry gas, 2 parts of polyoxyethylene group, 2 parts of polysiloxane group, 0.6 part of LiSO2CF3And 0.5 part of LiB (C)2O4)2Adding the mixture into a mixed solution (with the volume ratio of 1: 1) of acetonitrile and N-methylpyrrolidone, continuously stirring the mixture uniformly to obtain a slurry II, and adjusting the content of the mixed solution (with the volume ratio of 1: 1) of acetonitrile and N-methylpyrrolidone to 60 vol% of solid content;
step three: the first sizing agent corresponds to the front roller group, and the second sizing agent corresponds to the rear roller group;
step four: coating the first slurry on two sides of the current collector by the aid of the front roller group, wherein the coating thickness of the first slurry is 70 micrometers, coating the second slurry on the surface of the first slurry on two sides of the current collector by the aid of the rear roller group, and the coating thickness of the second slurry is 20 micrometers, so that a prefabricated module is obtained;
step five: drying the prefabricated module at the temperature of 90 ℃ for 1h synchronously, and then synchronously rolling to obtain an all-solid-state battery integrated module with a sheet structure of solid electrolyte/electrode/current collector/electrode/solid electrolyte;
here, 8 parts of double-sided NCA, 2 parts of carbon black, 0.6 part of LiSO2CF30.5 part of LiB (C)2O4)2Adding 2 parts of polyoxyethylene and 2 parts of polysiloxane into a mixed solution (volume ratio is 1: 1) of acetonitrile and N-methyl pyrrolidone, uniformly mixing, coating the mixed solution on a copper foil, paving the copper foil and the all-solid-state battery integrated module, and repeatedly laminating to obtain an all-solid-state battery cell. Here, the thickness of the solid electrolyte after drying was about 6 μm.
Example seven:
a preparation method of an all-solid-state battery integrated module comprises the following steps:
the method comprises the following steps: in the case of dry gas, 8 parts of NaxNiO21 part of carbon black, 0.6 part of NaN (SO)2CF3)20.5 part of NaClO4Adding 2 parts of polycarbonate and 2 parts of polymer lithium single-ion conductor into a mixed solution (volume ratio of 1: 1) of tetrahydrofuran and ethylene glycol dimethyl ether, uniformly stirring to obtain a first slurry, and adjusting the content of the mixed solution (volume ratio of 1: 1) of tetrahydrofuran and ethylene glycol dimethyl ether to 60 vol% of solid content;
step two: in the case of a dry gas, 2 parts of polycarbonate base, 2 parts of polymeric lithium single-ion conductor, 0.6 part of NaN (SO)2CF3)2And 0.5 part of NaClO4Adding the mixture into a mixed solution (volume ratio of 1: 1) of tetrahydrofuran and ethylene glycol dimethyl ether, continuously stirring uniformly to obtain a slurry II, and adjusting the content of the mixed solution (volume ratio of 1: 1) of tetrahydrofuran and ethylene glycol dimethyl ether to a solid content of 45 vol%;
step three: the first sizing agent corresponds to the front roller group, and the second sizing agent corresponds to the rear roller group;
step four: coating the first slurry on two sides of the current collector by the aid of the front roller group, wherein the coating thickness of the first slurry is 50 micrometers, coating the second slurry on the surface of the first slurry on two sides of the current collector by the aid of the rear roller group, and the coating thickness of the second slurry is 30 micrometers, so that a prefabricated module is obtained;
step five: drying the prefabricated module at the temperature of 80 ℃ for 8 hours synchronously, and then synchronously rolling to obtain an all-solid-state battery integrated module with a sheet-shaped structure of solid electrolyte/electrode/current collector/electrode/solid electrolyte;
here, 8 parts of sodium metal as a negative electrode was spread out with the above all-solid-state battery integrated module, and wound to obtain an all-solid-state battery cell. Here, the thickness of the solid electrolyte after drying is about 10 μm. Further, M may be one of Mn, Fe, Co and Cu.
Example eight:
a preparation method of an all-solid-state battery integrated module comprises the following steps:
the method comprises the following steps: in the case of dry gas, 9 parts of NaxMn(CN)61.5 parts of carbon black and 0.9 part of NaSO2CF31.1 parts of NaB (C)2O4)2Adding 1 part of polyoxyethylene and 2 parts of polysiloxane into a mixed solution (volume ratio of 1: 1) of tetrahydrofuran and acetonitrile, uniformly stirring to obtain a first slurry, and adjusting the content of the mixed solution (volume ratio of 1: 1) of tetrahydrofuran and acetonitrile to 75 vol% of solid content;
step two: in the case of dry gas, 1 part of polyoxyethylene group, 2 parts of polysiloxane group, 0.9 part of NaSO2CF3And 1.1 parts of NaB (C)2O4)2Adding the mixture into a mixed solution (with the volume ratio of 1: 1) of tetrahydrofuran and acetonitrile, continuously and uniformly stirring to obtain a slurry II, and adjusting the content of the mixed solution (with the volume ratio of 1: 1) of tetrahydrofuran and acetonitrile to 60 vol% of solid content;
step three: the first sizing agent corresponds to the front roller group, and the second sizing agent corresponds to the rear roller group;
step four: coating the first slurry on two sides of the current collector by the aid of the front roller group, wherein the coating thickness of the first slurry is 30 micrometers, coating the second slurry on the surface of the first slurry on two sides of the current collector by the aid of the rear roller group, and the coating thickness of the second slurry is 20 micrometers, so that a prefabricated module is obtained;
step five: drying the prefabricated module at the temperature of 100 ℃ for 6 hours synchronously, and then synchronously rolling to obtain an all-solid-state battery integrated module with a sheet-shaped structure of solid electrolyte/electrode/current collector/electrode/solid electrolyte;
here, 8 parts of a double-sided hard carbon material, 1.5 parts of carbon black, 0.9 part of NaSO2CF31.1 parts of NaB (C)2O4)2Adding 1 part of polyoxyethylene group and 2 parts of polysiloxane group into a mixed solution (volume ratio is 1: 1) of tetrahydrofuran and acetonitrile, uniformly mixing, coating the mixed solution on a copper foil, paving the copper foil and the all-solid-state battery integrated module, and repeatedly laminating to obtain an all-solid-state battery cell. Here, the thickness of the solid electrolyte after drying is about 5 μm. Further, M may be one of Ni, Fe, Co and Cu.
Comparative example one:
the method comprises the following steps: under the protection of dry gas, 8 parts of LFP, 1.5 parts of carbon black, 1.1 parts of LiB (C)2O4)2And 3 parts of polyoxyethylene group are added into acetonitrile, the mixture is uniformly stirred to obtain a first slurry, and the acetonitrile content is adjusted until the solid content is 75 vol%;
step two: uniformly scraping the slurry on an aluminum foil, and drying to obtain an anode layer;
step three: under the protection of dry gas, 3 parts of polyoxyethylene group and 1.1 part of LiB (C)2O4)2Adding the mixture into acetonitrile, continuously stirring the mixture evenly to obtain slurry III, and adjusting the acetonitrile content until the solid content is 45 vol%; (ii) a
Step four: and (3) casting the slurry III on a large-area smooth plane, evaporating the solvent to dryness, forming a film, and removing the film to obtain the polymer electrolyte film, wherein the film thickness is required to be higher than 50 micrometers in order to ensure the integrity of the film.
Step five: and laminating a polymer electrolyte film on the positive electrode layer, laminating a metal sodium negative electrode, and winding to assemble the all-solid-state battery.
Comparative example two:
the method comprises the following steps: under the protection of dry gas, 7 parts of lithium-rich, 1.5 parts of carbon black and 2 parts of LiSO2CF3And 5 parts of polymer lithium single-ion conductor, adding the polymer lithium single-ion conductor into N-methylpyrrolidone, uniformly stirring to obtain a first slurry, and adjusting the content of the N-methylpyrrolidone to 60 vol% of solid content;
step two: uniformly scraping the slurry I on an aluminum foil, and drying to obtain an anode layer;
step three: under the protection of dry gas, 7 parts of graphite, 1.5 parts of carbon black and 2 parts of LiClO4Adding 1 part of polymer lithium single-ion conductor into N-methyl pyrrolidone, and mixing uniformly to obtain slurry II;
step four: uniformly scraping the slurry II on a copper foil, and drying to obtain a negative electrode layer;
step five: 5 parts of polymer lithium single-ion conductor and 0.2 part of LiSO2CF3Adding the mixture into N-methyl pyrrolidone, continuously stirring the mixture evenly to obtain a third solution, and adjusting the content of the N-methyl pyrrolidone to 60 vol% of solid content;
step six: casting the slurry III on a large-area smooth plane, evaporating the solvent to dryness, forming a film, and removing the film to obtain a polymer electrolyte film, wherein the thickness of the film is required to be higher than 50 mu m in order to ensure the integrity of the film;
step seven: on the positive electrode layer, a polymer electrolyte film was laminated, and then the negative electrode layer was laminated, followed by repeated lamination to assemble an all-solid battery.
Comparative example three:
the method comprises the following steps: under the protection of dry gas, 9 parts of NaxMn(CN)61.5 parts of carbon black, 2 parts of LiSO2CF31.1 parts of NaB (C)2O4)2Adding 1 part of polyoxyethylene and 2 parts of polysiloxane into a mixed solution (volume ratio of 1: 1) of tetrahydrofuran and acetonitrile, uniformly stirring to obtain a first slurry, and adjusting the content of the mixed solution (volume ratio of 1: 1) of tetrahydrofuran and acetonitrile to 75 vol% of solid content;
step two: uniformly scraping the slurry I on an aluminum foil, and drying to obtain an anode layer;
step three: under the protection of dry gas, 8 parts of double-sided hard carbon material, 1.5 parts of carbon black and 0.9 part of NaSO2CF31.1 parts of NaB (C)2O4)2Adding 1 part of polyoxyethylene and 2 parts of polysiloxane into a mixed solution (volume ratio is 1: 1) of tetrahydrofuran and acetonitrile, and uniformly mixing to obtain slurry II;
step four: uniformly scraping the slurry II on a copper foil, and drying to obtain a negative electrode layer;
step five: 1 part of polyoxyethylene group, 2 parts of polysiloxane group and 0.9 part of NaSO2CF3And 1.1 parts of NaB (C)2O4)2Adding the mixture into a mixed solution (with the volume ratio of 1: 1) of tetrahydrofuran and acetonitrile, continuously and uniformly stirring to obtain a solution III, wherein the content of the mixed solution (with the volume ratio of 1: 1) of tetrahydrofuran and acetonitrile is up to 60 vol% of solid content;
step six: casting the slurry III on a large-area smooth plane, evaporating the solvent to dryness, forming a film, and removing the film to obtain a polymer electrolyte film, wherein the thickness of the film is required to be higher than 50 mu m in order to ensure the integrity of the film;
step seven: and laminating a polymer electrolyte film on the positive electrode layer, laminating the negative electrode layer, and repeatedly laminating to assemble the all-solid-state battery.
Testing the performance of the battery:
the capacity retention rates of all-solid-state batteries and the changes in the internal resistances of the batteries of examples one to eight, and comparative examples one to three were tested at 60 c, as shown in table two below.
Capacity retention rate and internal resistance of all-solid-state battery
Figure BDA0001669002760000121
As can be seen from the second table above, the all-solid battery cell of the present invention still has a comparatively high capacity retention rate after 1000 cycles. Meanwhile, when the first, fourth and eighth examples are compared with the first to third comparative examples, respectively, it can be seen that the internal resistance of the all-solid battery cell of the present invention is relatively small, and the increase in the internal resistance of the battery after 1000 cycles is relatively small, which means that the interfacial resistance of the battery cell is also relatively small. Therefore, the all-solid-state battery produced by the all-solid-state battery core is suitable for multiple fields.
Example nine:
an all-solid battery mainly uses a core body 1 of a battery cell made of an all-solid battery integrated module of any one of examples one to eight, where the core body 1 is divided into two types of a laminated type and a wound type. As shown in fig. 3, in the case of the all-solid-state battery in which the core 1 is of a laminated type, that is, the all-solid-state battery integrated module 11, the counter electrode 12 is laminated. As shown in fig. 4, the same all-solid-state battery integrated module 11 and counter electrode 12 are then repeated successively above until the desired thickness of the core 1 is stacked. The battery mainly comprises an aluminum-plastic film 2, wherein the core body 1 is arranged in the aluminum-plastic film 2 to obtain the all-solid-state battery, the aluminum-plastic film 2 is provided with a positive electrode end 3a and a negative electrode end 3b, and the positive electrode end 3a and the negative electrode end 3b are respectively connected with a positive electrode material and a negative electrode material.
As shown in fig. 5, in the all-solid-state battery in which the core 1 is wound, the counter electrode 12 is laminated on the all-solid-state battery integrated module 11, and then wound. The battery mainly comprises a shell 4, wherein the core body 1 is arranged in the shell 4 to obtain the all-solid-state battery, the end part of the shell 4 is also provided with a positive end II 5a and a negative end II 5b, and the positive end II 5a and the negative end II 5b are respectively connected with the positive material and the negative material of the core body 1.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (9)

1. An all-solid-state battery integration module, characterized in that: the solid electrolyte and the electrode which are positioned on the same side of the current collector (112) are integrally solidified into an integrated module (111);
the preparation method comprises the following steps:
the method comprises the following steps: under the condition of dry gas, stirring 1-2 parts of carbon black, 7-9 parts of electrode active material, 0.2-2 parts of alkali metal salt, 1-5 parts of polymer matrix and anhydrous solvent in vacuum according to parts by mass to obtain a first slurry;
step two: under the condition of dry gas, stirring 0.2-2 parts by mass of alkali metal salt, 1-5 parts by mass of polymer matrix and anhydrous solvent in vacuum to obtain slurry II;
step three: and sequentially and uniformly coating the first slurry and the second slurry on two sides of the current collector, synchronously drying at 80-100 ℃ for 1-8 hours, synchronously rolling and synchronously winding to obtain the integrated module sequentially comprising the solid electrolyte, the electrode, the current collector, the electrode and the solid electrolyte.
2. The all-solid-state battery integration module according to claim 1, characterized in that: the thickness of the solid electrolyte is 5-10 μm.
3. The all-solid-state battery integration module according to claim 1, characterized in that: the electrode active material can be any one of a positive electrode active material and a negative electrode active material, the positive electrode active material can be any one of a lithium ion electrode material and a sodium ion electrode material, and the negative electrode active material can be graphite or a silicon carbon material.
4. The all-solid-state battery integration module according to claim 3, characterized in that: the lithium ion electrode material may be any one of LFP, NCA, NCM, and lithium-rich.
5. An all solid state power supply as claimed in claim 3Pool integration module, its characterized in that: the sodium ion electrode material may be NaxMO2And NaxM(CN)6And M may be any one of Ni, Mn, Fe, Co and Cu.
6. The all-solid-state battery integration module according to claim 1, characterized in that: the polymer matrix can be any one or a mixture of more of polyoxyethylene, polycarbonate, polysiloxane and polymer lithium single-ion conductors.
7. The all-solid-state battery integration module according to claim 1, characterized in that: the alkali metal salt may be any one of a lithium salt and a sodium salt, and the lithium salt may be LiN (SO)2CF3)2、LiClO4、LiSO2CF3And LiB (C)2O4)2Any one or a mixture of several of the above, and the sodium salt can be NaN (SO)2CF3)2、NaClO4、NaSO2CF3And NaB (C)2O4)2Any one or a mixture of several of them.
8. The all-solid-state battery integration module according to claim 1, characterized in that: the anhydrous solvent can be any one or a mixture of more of acetonitrile, tetrahydrofuran, glycol dimethyl ether and N-methylpyrrolidone.
9. An all-solid-state battery characterized by: an all-solid-state battery integration module (11) comprising any one of claims 1 to 8.
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