CN110120510B - All-solid-state battery and preparation method thereof - Google Patents
All-solid-state battery and preparation method thereof Download PDFInfo
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- CN110120510B CN110120510B CN201910436104.XA CN201910436104A CN110120510B CN 110120510 B CN110120510 B CN 110120510B CN 201910436104 A CN201910436104 A CN 201910436104A CN 110120510 B CN110120510 B CN 110120510B
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- 239000007784 solid electrolyte Substances 0.000 claims abstract description 90
- 239000006258 conductive agent Substances 0.000 claims abstract description 48
- 229910003092 TiS2 Inorganic materials 0.000 claims abstract description 40
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- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 125000000101 thioether group Chemical group 0.000 claims abstract description 11
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
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- 239000007774 positive electrode material Substances 0.000 abstract description 45
- 150000002500 ions Chemical class 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 15
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- 239000000178 monomer Substances 0.000 description 6
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- 239000012448 Lithium borohydride Substances 0.000 description 5
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002203 sulfidic glass Substances 0.000 description 3
- 229910005842 GeS2 Inorganic materials 0.000 description 2
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 2
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 2
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 2
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- 241001391944 Commicarpus scandens Species 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910007307 Li2S:P2S5 Inorganic materials 0.000 description 1
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- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 230000001351 cycling effect Effects 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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Classifications
-
- 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
- H01M10/058—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an all-solid-state battery and a preparation method thereof. The all-solid-state battery of the present invention includes: a positive plate, a solid electrolyte layer and a negative plate; wherein, the positive plate comprises a current collector and a positive material layer, the positive material layer comprises a positive active material and an ion conductive agent, and the positive active material is TiS2The ionic conductive agent is sulfide; the solid electrolyte layer includes a solid electrolyte, and the solid electrolyte is a sulfide. The preparation method comprises the following steps: step S1: preparing a positive plate; step S2: preparing a solid electrolyte layer; step S3: and (3) placing the negative plate on the solid electrolyte layer, and then heating and pressurizing in vacuum to obtain the all-solid-state battery. The all-solid-state battery and the all-solid-state battery prepared by the method have the advantages of high energy density, good cycle performance and rate performance, and good battery capacity retention during self-sustaining voltage charging and discharging.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an all-solid-state battery and a preparation method thereof.
Background
In the existing all-solid-state battery, oxide is generally adopted as a positive electrode active material; sulfide with high deformability and high conductivity is used as the solid electrolyte.
However, it has the following technical problems:
(1) the potential difference exists between the anode active material of the oxide and the solid electrolyte of the sulfide, and a space charge layer is easy to generate, so that the interface resistance between the anode plate and the solid electrolyte layer is large, and the cycle performance and the rate capability of the all-solid battery are poor.
(2) The conventional oxides have low theoretical capacity of the positive active material (e.g., LiCoO)2The theoretical capacity of the catalyst is only 130mAh/g and LiFeO4A theoretical capacity of about 170mAh/g), which makes the energy density of the all-solid battery low.
(3) The sulfide solid electrolyte has high activity, and is easy to generate chemical reaction with the anode active material of the oxide, so that the performance of the all-solid battery is unstable.
At present, the powder tabletting method is generally adopted for preparing the all-solid-state battery, and the following problems exist in the method:
(1) the charging and discharging performance of the all-solid-state battery can be tested only by depending on pressurization of a pressurization device, once a mold is removed, the battery is easy to break and pulverize in the moving process, so that the internal impedance of the battery is too large, the battery capacity is quickly attenuated during charging and discharging, and if the pressurization device is used, the energy density of all-solid-state battery monomers is low.
(2) The solid electrolyte layer is thick (typically above 1 mm) making the energy density of the all-solid battery low.
Therefore, it is urgently needed to provide an all-solid-state battery and a preparation method thereof, wherein the all-solid-state battery has good rate capability, cycle performance and energy density, and can keep good battery capacity during charging and discharging under the condition of self-sustaining pressure.
Disclosure of Invention
The present invention provides a method of producing TiS2The all-solid-state battery is a positive electrode active material, and at least solves the problems that the all-solid-state battery in the prior art is high in interface impedance and low in battery cycle performance and rate capability, and the all-solid-state battery in the prior art is low in energy density.
The invention provides a preparation method of an all-solid-state battery coated with slurry and heated and pressurized under a vacuum condition, which at least solves the problems that the battery capacity of the all-solid-state battery prepared by a powder tabletting method in the prior art is rapidly attenuated under the condition of no pressurized die holding, and the energy density is low due to an excessively thick solid electrolyte layer.
According to an aspect of the present invention, there is provided an all-solid battery including: a positive plate, a solid electrolyte layer and a negative plate; wherein,
the positive plate comprises a current collector and a positive material layer, the positive material layer comprises a positive active material and an ion conductive agent, and the positive active material is TiS2The ionic conductive agent is sulfide;
the solid electrolyte layer includes a solid electrolyte that is a sulfide.
Alternatively, the TiS may be an all-solid-state battery according to the invention2The mass ratio of the ionic conductive agent to the ionic conductive agent is 1:0.3 to 3.
Alternatively, according to the all-solid-state battery of the invention, the sulfide is Li3PS4Or doping modified Li3PS4Wherein
the doping phase of doping modification is P, LiI, LiCl and P2S3、P2O5、Al2S3、GeS2、SiS2、SnS2And LiBH4Any one or a combination of several of them.
Alternatively, according to the all-solid-state battery of the present invention, the doping phase is in the doping-modified Li3PS4The mole percentage of (B) is 0.1-10%.
Optionally, according to the all-solid battery of the invention, the negative electrode sheet is a lithium sheet.
According to another aspect of the present invention, there is provided a method of manufacturing an all-solid battery, the method being performed in a vacuum or an inert atmosphere, comprising:
step S1: mixing TiS2Dissolving an ionic conductive agent and a binder in a solvent, blending to obtain positive electrode slurry, wherein the ionic conductive agent is sulfide, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain a positive electrode plate;
step S2: dissolving a solid electrolyte and a binder in a solvent, blending to obtain solid electrolyte slurry, wherein the solid electrolyte is sulfide, coating the solid electrolyte slurry on a positive plate, and drying to form a solid electrolyte layer;
step S3: and placing the negative plate on the solid electrolyte layer, and then heating and pressurizing in vacuum to obtain the all-solid-state battery.
Alternatively, according to the production method of the present invention, in the step S1, TiS2Mass ratio to the ion conductive agent 1: 0.3-3.
Optionally, according to the preparation method of the invention, in the step S1, the drying temperature is 30 to 80 ℃ and the time is 1 to 24 hours.
Alternatively, according to the preparation method of the present invention, in the step S2, the coating thickness of the solid electrolyte slurry is 200 to 500 μm.
Optionally, according to the preparation method of the present invention, in the step S2, the drying temperature is 30 to 80 ℃ and the time is 1 to 10 min.
Alternatively, according to the preparation method of the present invention, in the step S3, the negative electrode sheet is a lithium sheet and the degree of vacuum is 10-5～10-2MPa, temperature of 180 ℃ and pressure of 10-100MPa, and time of 0.5-10 h.
Advantageous effects
The all-solid-state battery according to the present invention employs TiS2As the positive active material, on one hand, the interface resistance of the all-solid-state battery is reduced, and the cycle performance and the rate performance of the all-solid-state battery are improved; on the other hand, due to TiS2The method has excellent theoretical energy, and improves the energy density of the all-solid-state battery; in yet another aspect, TiS2Does not react with the sulfide solid electrolyte, thereby improving the stability of the all-solid battery.
According to the method for producing an all-solid-state battery of the present invention, since the slurry coating method is employed and heating and pressurizing are performed under vacuum conditions in step S3, an all-solid-state battery in which the battery capacity is kept good at the time of charging and discharging under self-sustaining pressure is produced.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention by way of the following detailed description.
According to an aspect of the present invention, there is provided an all-solid battery including: a positive plate, a solid electrolyte layer and a negative plate; wherein,
the positive plate comprises a current collector and a positive material layer, wherein the positive material layer comprises a positive active material and an ion conductive agent, and the positive active material is TiS2The ionic conductive agent is sulfide;
the solid electrolyte layer includes a solid electrolyte, and the solid electrolyte is a sulfide.
The all-solid-state battery of the invention, in one aspect, TiS2And the solid electrolyte is sulfide to form a sulfide-sulfide interface, so that the interface compatibility between the positive electrode material layer of the positive plate and the solid electrolyte layer is improved, and the interface impedance between the positive plate and the solid electrolyte layer is effectively reduced.
On the other hand, TiS in the positive electrode material2And sulfide as ion conductive agent to form sulfide-sulfide interface to improve TiS2And the interface compatibility between the ionic conducting agent and the ionic conducting agent effectively reduces the interface impedance between the ionic conducting agent and the ionic conducting agent.
In yet another aspect, TiS2The mixed conductor is a solid conductive material between the ionic conductor and the electronic conductor, has ionic conductivity and electronic conductivity, and has quite high ionic conductivity and electronic conductivity, so that when the anode slurry is manufactured, a conductive agent (Super P and the like) does not need to be additionally added, a material interface is reduced in the anode material layer, and the interface resistance in the anode material is reduced to a certain extent.
In conclusion, the positive active material adopts TiS2The interface impedance of the all-solid-state battery is reduced, and therefore the rate capability and the cycle performance of the all-solid-state battery are improved.
The all-solid-state battery adopts TiS2As a positive electrode active material, the theoretical capacity is 239mAhg～1Higher than that of the traditional positive active material (such as LiCoO)2Has a capacity of 130mAh/g, LiFeO4170mAh/g), thereby increasing the energy density of the all-solid battery.
All solid-state battery, TiS, of the invention2Does not react with the sulfide solid electrolyte, thereby improving the stability of the all-solid battery.
In some embodiments of the all-solid-state battery of the invention, TiS2The mass ratio to the ion conductive agent is preferably 1:0.3 to 3.
Of these, 1:0.3, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5 and 1:3 are typically, but not restrictively, preferred.
The sulfide serving as the ionic conductive agent on the positive electrode material layer of the positive electrode plate can form an ion migration channel on the positive electrode material layer, and the ionic conductivity of the positive electrode plate is improved.
In the positive electrode material layer, TiS2The mass ratio of the ionic conductive agent to the ionic conductive agent is 1: 0.3-3, if the mass ratio is less than 1:0.3, an ion migration channel in the positive electrode material layer is reduced, and the ionic conductivity of the positive electrode plate is reducedThe internal resistance of the positive electrode material layer is enabled to be overlarge; if the mass ratio is more than 1:3, TiS2Too small, a stable positive electrode material layer cannot be formed.
In some embodiments of the all-solid-state battery of the invention, the sulfide is preferably Li3PS4Or doping modified Li3PS4Wherein
the doping phase of doping modification is preferably P, LiI, LiCl, P2S3、P2O5、Al2S3、GeS2、SiS2、SnS2And LiBH4Any one or a combination of several of them.
In the all-solid-state battery of the invention, the ion conductive agent and the solid electrolyte are preferably the same sulfide.
When the ion conductive agent and the solid electrolyte adopt the same sulfide, the interface compatibility of the positive plate and the solid electrolyte layer is improved and the interface impedance is reduced compared with the case of adopting different sulfides.
The sulfide used as the ion conductive agent may be the same as or different from the sulfide used as the solid electrolyte, and one kind or a combination of two or more kinds may be used.
In the all-solid-state battery of the invention, the sulfide can be selected from Li2S～P2S5Doped modified Li2S～P2S5、Li2S～P2S5Glass phase or glass-ceramic phase, doped modified Li2S～P2S5Glass phase or glass-ceramic phase, Li10GeP2S12And doping modified Li10GeP2S12And the like, but other sulfides that can be used as the sulfide electrolyte may be used.
Wherein Li2S～P2S5Indicating that the preparation raw materials comprise Li in different molar ratios2S and P2S5For example, including: 75Li2S～25P2S5、70Li2S～30P2S5、80Li2S～20P2S5Etc., which of course is not limited to these ratios, and includes all sulfides that may be used, consisting of the two in different molar ratios.
In addition, Li is selected2S-P2S5Glassy phase or doped modified Li2S-P2S5In the glass phase, phase transition occurs during high-temperature drying, so that the phase state is not limited compared with that of Li2S-P2S5The ion conductivity of the all-solid battery is improved.
In the present invention Li3PS4And 75Li2S～25P2S5Represented by the same sulfide except for 75Li2S～25P2S5The representation shows that the molar ratio of the raw materials used in the preparation of the sulphide is 75: 25; li3PS4The representation shows the sulfide product produced.
The different properties of the all-solid battery can be improved by doping different dopants.
For example: when the dopant contains F or Cl, the dopant and the lithium cathode can form a protective layer with high Young modulus such as LiF, LiCl and the like, so that the growth of lithium dendrites is prevented, and the increase of the internal resistance of the all-solid-state battery is avoided.
The sulfide can be prepared by the following method: under the protection of inert atmosphere, P is added2S5、Li2And mixing S and the dopant in proportion, sealing the mixture in a sealed container, and placing the sealed container in microwave for microwave treatment to obtain the sulfide.
Through doping modification of the sulfide, defects are introduced into the sulfide, so that the ionic conductivity of the sulfide is improved, and the ionic conductivity of the all-solid-state battery is further improved.
For example: the doping phase is LiCl, and LiCl occupies doping modified Li3PS4Is 3%, (i.e. 97 Li)3PS43LiCl) which was measured to have an ionic conductivity of 4.3X 10 at room temperature after tableting-3Scm-1. The ionic conductivity of the alloy is Li before doping modification3PS4Measured under the same conditions5 times the ionic conductivity of (a).
In one embodiment of the invention, the sulfides as solid electrolyte are LiCl and LiBH4Doping modified Li3PS4On one hand, the ionic conductivity of the all-solid-state battery can be improved, and on the other hand, when the negative plate is a lithium plate, the stability of the negative plate can be improved.
In some embodiments of the all-solid-state battery of the invention, the doping phase is doping modified Li3PS4The mole percentage of (B) is 0.1-10%, preferably 2-4%.
Wherein the doping phase is doped with modified Li3PS4Typically but not limitatively preferred is 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% and 10%.
In some embodiments of the all-solid-state battery, the negative plate is a lithium plate, and the lithium plate is selected, so that on one hand, the performance of the all-solid-state battery can be improved by doping modified sulfide; on the other hand, the lithium sheet is selected, and in the preparation process, after the melting temperature of the lithium sheet is reached, the lithium sheet can be melted and tightly combined with the solid electrolyte layer, so that normal charge and discharge under a self-sustaining pressure state are realized.
According to another aspect of the present invention, there is provided a method of manufacturing an all-solid battery, the method being performed in a vacuum or an inert atmosphere, comprising:
step S1: mixing TiS2Dissolving an ion conductive agent and a binder in a solvent, blending to obtain positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, drying to obtain a positive electrode plate,
step S2: dissolving a solid electrolyte and a binder in a solvent, blending to obtain solid electrolyte slurry, wherein the solid electrolyte is sulfide, and coating the solid electrolyte on a positive plate and drying to form a solid electrolyte layer;
step S3: and placing the negative plate on the solid electrolyte layer, and then heating and pressurizing in vacuum to obtain the all-solid-state battery.
According to the method for manufacturing an all-solid-state battery of the present invention, an all-solid-state battery capable of normal charge and discharge under self-sustaining pressure is manufactured by applying a slurry coating method and heating under vacuum in step S3.
In steps S1 and S2, the binders in the positive electrode slurry and the solid electrolyte slurry may be the same or different.
The binder is preferably at least one of polypropylene carbonate, styrene-butadiene rubber, nitrile rubber or silicone rubber.
In step S1, the mass of the binder is TiS22-8% of the total mass of the ionic conductive agent, wherein 2%, 3%, 4%, 5%, 6%, 7% and 8% are typically but not restrictively preferred.
In step S2, the mass of the binder is 2-8% of the mass of the solid electrolyte, with 2%, 3%, 4%, 5%, 6%, 7%, and 8% being typically but not limited to preferred.
In step S1 and step S2, the solvents may be the same or different.
The solvent is preferably tetrahydrofuran, anisole, toluene, xylene or 1, 2-dichloroethane.
When the solvent is Tetrahydrofuran (THF) and the negative plate is a lithium plate, a uniform and compact passivation film can be formed on the lithium plate, so that the stability of the lithium plate is improved, the side reaction between the negative plate and the solid electrolyte layer is inhibited, the interface impedance between the solid electrolyte layer and the lithium plate is reduced, and the rate capability and the cycling stability of the all-solid-state battery are improved.
In steps S1 and S2, the amount of solvent used is preferably 10 to 50 times the mass of the solvent, typically but not limited to 10 times, 15 times, 20 times, 25 times, 30 times, 35 times, 40 times, 45 times, and 50 times the mass of the binder.
Wherein, after the positive electrode layer is coated in steps S1 and S2, the solid electrolyte layer is coated; however, the order of preparing the positive electrode slurry and the solid electrolyte slurry is not limited. The anode slurry can be prepared first, and then the solid electrolyte slurry can be prepared; or preparing the solid electrolyte slurry first and then preparing the anode slurry.
The sequence may be in the order: preparing anode slurry, coating the anode slurry, preparing solid electrolyte slurry, and coating the solid electrolyte slurry.
The sequence can also be as follows: preparing anode slurry, preparing solid electrolyte slurry, coating the anode slurry and coating the solid electrolyte slurry.
The sequence can also be as follows: preparing solid electrolyte slurry, preparing anode slurry, coating the anode slurry and coating the solid electrolyte slurry.
Therefore, the order of preparing the cathode slurry and the solid electrolyte slurry is not strictly limited in the present invention, and those skilled in the art can implement the technical solution of the present invention according to the order used conventionally.
In some embodiments of the preparation method of the present invention, in step S1, TiS2Mass ratio to the ion conductive agent 1: 0.3-3.
Of these, 1:0.3, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5 and 1:3 are typically, but not restrictively, preferred.
The sulfide serving as the ionic conductive agent on the positive electrode material layer of the positive electrode plate can form an ion migration channel on the positive electrode material layer, so that the ionic conductivity of the positive electrode plate is improved.
In the positive electrode material layer, TiS2The mass ratio of the ionic conductive agent to the ionic conductive agent is preferably 1: 0.3-3, if the mass ratio is less than 1:0.3, an ion migration channel in the positive electrode material layer can be reduced, so that the ionic conductivity of the positive electrode plate is reduced, and the internal resistance of the positive electrode material layer is overlarge; if the mass ratio is more than 1:3, TiS2Too small, a stable positive electrode material layer cannot be formed.
In some embodiments of the preparation method of the present invention, in step S1, the drying temperature is 30-80 ℃ and the drying time is 1-24 hours.
Among them, the drying temperature is typically, but not restrictively, preferably 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃.
Drying times are typically, but not exclusively, preferably 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h and 24 h.
In step S1, the solvent in the positive electrode slurry can be partially removed under the above conditions, and a part of the solvent remains therein, so that the positive electrode material layer and the solid electrolyte slurry coated thereon can have a good wetting effect, and thus dense bonding of the positive electrode material layer and the solid electrolyte layer can be achieved.
In step S1, the above operation may be performed in vacuum, or may be performed in an inert atmosphere, such as an argon atmosphere or a nitrogen atmosphere.
In step S1, the coating thickness of the positive electrode slurry is preferably 200 to 500 μm, and typically, but not limited to, 200um, 250um, 300um, 350um, 400um, 450um and 500um are preferable.
In some embodiments of the preparation method of the present invention, in step S2, the coating thickness of the solid electrolyte slurry is preferably 200 to 500 μm.
Among them, the coating thickness of the solid electrolyte slurry is typically, but not limitedly, preferably 200um, 250um, 300um, 350um, 400um, 450um and 500 um.
The coating thickness of the solid electrolyte slurry is within this range, and after drying to remove the solvent, the thickness becomes much thinner than the thickness (about 1 mm) of the solid electrolyte layer by the powder tableting method, and therefore the energy density of the all-solid battery can be improved.
According to some embodiments of the preparation method of the present invention, in step S2, the drying temperature is 30 to 80 ℃ and the drying time is 1 to 10 min.
Among them, the drying temperature is typically, but not restrictively, preferably 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃.
Drying times are typically, but not restrictively, preferably 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min and 10 min.
In step S2, a part of the solvent in the solid electrolyte slurry can be removed under the above conditions, and the drying is preferably performed until the electrolyte slurry does not flow around but the solvent is not completely removed.
In step S2, the solid electrolyte is directly coated on the positive electrode layer to form a film, so as to avoid the film from being broken during the transfer process.
In some embodiments of the preparation method of the present invention, in step S3, the negative electrode sheet is a lithium sheet and the degree of vacuum is 10-5～10-2MPa, heating temperature of 180 ℃ and temperature of 240 ℃, pressure of 10-100MPa and time of 0.5-10 h.
Wherein the vacuum is typically, but not limited to, preferably 10-5、10-4、10-3And 10-2MPa。
Wherein the heating temperature is typically, but not restrictively, preferably 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃ and 240 ℃.
The melting point of the lithium sheet is 180 ℃, because oxides generally exist on the surface of the lithium sheet, the melting point is slightly higher than 180 ℃, and the lithium sheet can be well melted at 180-240 ℃ under the vacuum pressurization condition, so that the lithium sheet and the solid electrolyte layer can be combined in situ, and the two layers are more compact. However, when the heating temperature is too high, the sulfide may be decomposed or an interfacial reaction may occur, thereby affecting the cycle performance of the battery.
Wherein the pressure is typically, but not limited to, preferably 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, 60MPa, 70MPa, 80MPa, 90MPa and 100 MPa.
Under the action of external pressure, the combination of the solid electrolytes, the positive active material and the ionic conductive agent in the positive material layer, the positive material layer and the solid electrolyte layer and the negative plate can be more compact, so that the all-solid-state battery has good capacity retention rate when the obtained all-solid-state battery is charged and discharged under the condition of self-sustaining pressure. .
Among them, in step S3, the time is typically, but not restrictively, preferably 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h and 10 h.
In step S3 of the present invention, the battery capacity is maintained well when the battery is charged and discharged in a self-sustaining state under the conditions of vacuum heating and pressurization. In which the self-sustaining pressure, that is, the all-solid battery does not rely on the external applied pressure, in other words, the all-solid battery does not employ a pressurizing mold or the like to pressurize it.
The present invention will be described in detail with reference to specific examples and comparative examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
In the following examples, sulfides were prepared by the following procedures.
(1)Li3PS4Preparation of
In an argon glove box, Li2S:P2S5According to a molar ratio of 3:1 proportion, sealing with quartz crucible, placing in microwave oven for 6min to obtain Li3PS4An electrolyte powder.
(3) Li doped with LiCl3PS4Preparation of
In a glove box, P is put2S5·Li2S is mixed according to the molar ratio of 3:1, LiCl is added and mixed evenly, a quartz crucible is used for sealing completely, the mixture is placed into a microwave oven for microwave for 5min, and gray LiCl-doped electrolyte 97Li is obtained3PS43LiCl, where Li3PS4The molar ratio to LiCl was 97: 3.
(4) The doping phases are LiCl and LiBH4Li of (2)3PS4Preparation of
In a glove box, P is put2S5·Li2S is mixed according to the molar ratio of 3:1, LiCl is added and mixed evenly, a quartz crucible is used for sealing completely, the mixture is placed into a microwave oven for microwave for 5min, and gray LiCl-doped electrolyte 97Li is obtained3PS4·3LiCl。
Then, 97Li was added3PS43LiCl electrolyte powder with LiBH4Fully mixing the powder according to the mass ratio of 70:30 to obtain LiCl and LiBH doped phases4Li of (2)3PS4。
Example 1
This embodiment provides a method for manufacturing an all-solid battery.
Step S1 is first performed: in an argon atmosphere, TiS2And dissolving the ionic conductive agent and the binder in a solvent, blending to obtain positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain the positive electrode plate.
Wherein the ion conductive agent is Li3PS4The adhesive is nitrile rubber, and the solvent is tetrahydrofuran.
In an argon glove box, TiS2、Li3PS4Mixing the powder according to the mass ratio of 1:1.5, adding the powder into tetrahydrofuran dissolved with nitrile butadiene rubber, fully stirring and mixing to obtain positive electrode slurry, wherein the mass of the nitrile butadiene rubber accounts for TiS2And Li3PS46 percent of the total mass, wherein the mass of the solvent is 20 times of that of the nitrile rubber.
And coating the positive electrode slurry on an aluminum foil (positive electrode current collector) to obtain a positive electrode plate, wherein the coating thickness is 300 mu m, the drying temperature is 65 ℃, and the time is 12 hours.
Step S2: and dissolving the solid electrolyte and the binder in a solvent, blending to obtain solid electrolyte slurry, wherein the solid electrolyte is sulfide, and coating the solid electrolyte slurry on the positive plate and drying to form a solid electrolyte layer.
Wherein the sulfide is Li3PS4The adhesive is nitrile rubber, and the solvent is tetrahydrofuran.
Wherein the nitrile rubber is mixed with Li3PS4The mass percent of the solvent is 6 percent, and the mass of the solvent is 20 times of that of the nitrile rubber.
In an argon glove box, Li3PS4And uniformly dispersing the nitrile rubber and the butadiene-acrylonitrile rubber in tetrahydrofuran to obtain solid electrolyte slurry, directly blade-coating the solid electrolyte slurry to the positive plate obtained in the step S1, wherein the thickness of the positive plate is 300 mu m, and drying the positive plate at 60 ℃ for 5min to obtain a solid electrolyte layer.
Step S3: and placing the negative plate on the solid electrolyte layer, and heating and pressurizing in vacuum to obtain the all-solid-state battery.
Placing a lithium plate (negative plate) on the solid electrolyte layer under a vacuum degree of 10-3And (3) carrying out heat treatment for 2h at the temperature of 180 ℃ under Mpa, and applying the pressure of 20MPa among the positive plate, the solid electrolyte layer and the lithium plate during the heat treatment to obtain the battery cell monomer of the all-solid-state battery.
Example 2
The other parameters of this example were the same as example 1, except that TiS2The mass ratio of the ionic conductive agent to the ionic conductive agent is 1: 0.3.
example 3
The other parameters of this example were the same as example 1, except that TiS2The mass ratio of the ionic conductive agent to the ionic conductive agent is 1:2.
example 4
The other parameters of this example were the same as example 1, except that TiS2The mass ratio of the ionic conductive agent to the ionic conductive agent is 1: 3.
example 5
The other parameters of this example were the same as those of example 1 except that the temperature in step S2 was 30 ℃.
Example 6
The other parameters of this example were the same as those of example 1 except that the temperature in step S2 was 50 ℃.
Example 7
The other parameters of this example were the same as those of example 1 except that the temperature in step S2 was 80 ℃.
Example 8
The other parameters of this example were the same as those of example 1 except that the temperature in step S3 was 190 ℃.
Example 9
The other parameters of this example were the same as those of example 1 except that the temperature in step S3 was 220 ℃.
Example 10
The other parameters of this example were the same as those of example 1 except that the temperature in step S3 was 240 ℃.
Example 11
This embodiment is as followsThe other parameters of example 1 were the same except that the sulfide was Li in LiCl as the doping phase obtained in the above preparation3PS4。
Example 12
The example is identical to example 1 with respect to the other parameters, except that the sulphide is LiCl and LiBH, as doping phases obtained by the above preparation4Li of (2)3PS4。
Comparative example 1
The comparative example was identical to example 1 in all other parameters except that the positive electrode active material was LiCoO2。
Comparative example 2
This comparative example was prepared using powder tableting directly, with the same parameters as example 1, except that no slurry was made.
Mixing TiS2Powder with Li3PS4The powder is weighed according to the proportion of 1:1.5, and is ground and mixed to form the composite anode powder.
First, 120mgLi was taken3PS4Pressing the powder in a mould under 72MPa to form a disc-shaped solid electrolyte layer with the diameter of 10mm, then uniformly placing 30mg of composite anode powder on one surface of the solid electrolyte layer, pressing under 370MPa, finally placing a lithium sheet on the other surface of the solid electrolyte layer, pressing under 370MPa to prepare a battery core monomer of the all-solid battery, taking out the battery core monomer from the mould, and placing the battery core monomer into a button-type battery case for electrochemical test.
Comparative example 3
The comparative example was identical to example 1 in all other parameters except that TiS2The mass ratio of the ionic conductive agent to the ionic conductive agent is 1: 0.2.
comparative example 4
The comparative example was identical to example 1 in all other parameters except that TiS2The mass ratio of the ionic conductive agent to the ionic conductive agent is 1: 4.
comparative example 5
The comparative example was identical to example 1 in all other parameters except that the heating temperature in step S3 was 160 ℃.
Comparative example 6
The comparative example was identical to example 1 in all other parameters except that the heating temperature in step S3 was 250 ℃.
The all-solid-state batteries obtained in examples 1 to 12 and comparative example 1 were left at room temperature for a certain period of time to test the ac impedance of the batteries.
The test method is as follows: and assembling the obtained cell monomers of the all-solid-state battery into a button battery, then carrying out alternating current impedance test on the button battery at a Chenghua electrochemical workstation, and recording alternating current impedance after the button battery is placed at room temperature for different times so as to research the interface impedance change of the all-solid-state battery. The potential amplitude of the alternating current impedance test is 5mV, the frequency range is 100 kHz-0.1 Hz, and the test results are shown in Table 1.
TABLE 1
As can be seen from examples 1 to 12 in Table 1, the all-solid-state battery of the present invention has a small change in impedance with time and good impedance stability.
As can be seen from example 1 and comparative example 1, TiS was used2As a positive electrode active material, LiCoO was used in comparison2As the positive electrode active material, the impedance of the all-solid battery can be significantly reduced.
The all-solid-state batteries obtained in examples 1 to 12 and comparative examples 1 to 8 were subjected to tests of cycle performance and energy density.
Assembling the obtained all-solid-state battery cell into a button cell, and then carrying out charge-discharge and cycle performance tests on a LAND CT2001A tester, wherein TiS2The test voltage range of (1.0-2.5) V, LiCoO2The test voltage interval is 3.0-4.2V, and the test current density is 0.1C; the specific capacity was calculated based on the mass of the positive active material in the composite positive electrode, and it should be specifically noted that the test of the all-solid battery of comparative example 2 was a cycle test conducted under the condition that the mold was kept but no external pressure was applied (i.e., the all-solid battery was not taken out of the mold, and was prevented from moving, but no external pressure was applied), and the test results were as shown in table 2.
TABLE 2
As can be seen from Table 2, example 1 and comparative example 1, LiCoO was used2When the lithium ion battery is used as a positive electrode active material, the capacity of the all-solid-state battery is changed into 0 when the lithium ion battery is cycled for 5 times due to poor interface compatibility and high interface impedance; while using TiS2As the positive electrode active material, the interfacial impedance of the all-solid-state battery is reduced, the battery capacity can still reach 225mAh/g after the battery is cycled for 100 times, and the capacity retention rate of the battery is up to 91.8 percent after the battery is cycled for 100 times, so that the cycle performance of the all-solid-state battery is improved.
It can also be seen from example 1 and comparative example 1 that TiS was used2As a positive electrode active material, the theoretical capacity of the material is 239mAhg～1Higher than LiCoO2Thereby increasing the energy density of the all-solid battery by 130 mAh/g.
As can be seen from example 1 and comparative example 2, the all-solid battery obtained in example 1 was charged and discharged without external pressure applied by a pressurizing mold, and the capacity retention rate thereof reached 91.8%; in contrast, comparative example 2, which was charged and discharged without the external pressure applied by the pressurizing mold, the battery capacity rapidly decayed to 0.
As can be seen from examples 1 to 4 and comparative examples 3 and 4, TiS2When the mass ratio of the lithium ion battery to the ionic conductive agent is 1: 0.3-3, a good ion channel is constructed in the positive electrode material, so that the ionic conductivity of the battery can be improved, and the cycle performance of the battery is improved.
As can be seen from examples 1, 8 to 10, and comparative examples 5 and 6, in step S3, the cycle performance of the all-solid battery was good when the heating temperature was in the range of 180 to 240 ℃.
In summary, it can be seen that the all-solid-state battery of the present invention, in one aspect, TiS2And sulfide solid state electricityThe electrolytes are all sulfides to form a sulfide-sulfide interface, so that the interface compatibility between the positive plate and the solid electrolyte layer is improved, and the interface impedance between the positive plate and the solid electrolyte layer is effectively reduced; on the other hand, TiS in the positive electrode material2And sulfide as ion conductive agent to form sulfide-sulfide interface, and improve TiS2The ionic conductive agent is compatible with the interface between the ionic conductive agent and the metal material, so that the interface impedance between the ionic conductive agent and the metal material is effectively reduced; on the other hand, TiS used2Has high ionic conductivity and electronic conductivity (ca.10)4S cm-1) Therefore, a conductive agent (Super P and the like) does not need to be additionally added into the positive electrode material, so that one material interface is reduced in the positive electrode material, and the interface resistance in the positive electrode material is also reduced to a certain extent; therefore, the positive electrode active material employs TiS2The interface impedance of the all-solid-state battery is reduced, and therefore the rate capability and the cycle performance of the all-solid-state battery are improved.
The all-solid-state battery adopts TiS2As a positive electrode active material, the theoretical capacity is 239mAhg～1Far higher than that of the traditional positive active material (such as LiCoO)2Capacity of 130mAh/g, LiFeO4170mAh/g), thereby increasing the energy density of the all-solid battery.
According to the preparation method, the positive electrode slurry is coated on the current collector by a coating method and dried to obtain the positive electrode plate, the solid electrolyte slurry is coated on the positive electrode plate, the negative electrode plate is stacked on the solid electrolyte layer and then heated, pressurized and dried under the vacuum condition, and the battery capacity of the obtained all-solid-state battery is kept well when the all-solid-state battery is charged and discharged under self-holding pressure.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (1)
1. A method of making an all-solid-state battery, carried out in a vacuum or inert atmosphere, comprising:
step S1: mixing TiS2Dissolving an ionic conductive agent and a binder in a solvent, blending to obtain positive electrode slurry, wherein the ionic conductive agent is sulfide, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain a positive electrode plate; TiS2Mass ratio to the ionic conductive agent of 1:0.3 to 3; the sulfide is doped and modified Li3PS4The doping phase is LiCl, and the doping mole percentage of the LiCl is 3 percent; the drying temperature is 30-80 ℃, and the drying time is 1-24 hours;
step S2: dissolving a solid electrolyte and a binder in a solvent, blending to obtain a solid electrolyte slurry, wherein the solid electrolyte is sulfide, coating the solid electrolyte slurry on the positive plate, and drying to form a solid electrolyte layer; the drying temperature is 30-80 ℃, and the drying time is 1-10 min;
in step S1 and step S2, the solvent is the same, and is tetrahydrofuran;
step S3: placing the negative plate on the solid electrolyte layer, and then heating and pressurizing in vacuum to obtain an all-solid-state battery; the negative plate is a lithium plate with a vacuum degree of 10-5～10-2MPa, temperature of 210 ℃ and 240 ℃, pressure of 10-100MPa and time of 0.5-10 h.
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| CN114203992B (en) * | 2021-12-07 | 2024-01-30 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
| CN116666566A (en) * | 2022-01-29 | 2023-08-29 | 天目湖先进储能技术研究院有限公司 | TiS (titanium sulfide) 2 Composite positive electrode and all-solid-state battery device |
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