CN109301342A - A kind of all-solid-state battery and preparation method thereof - Google Patents
A kind of all-solid-state battery and preparation method thereof Download PDFInfo
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- CN109301342A CN109301342A CN201811229496.4A CN201811229496A CN109301342A CN 109301342 A CN109301342 A CN 109301342A CN 201811229496 A CN201811229496 A CN 201811229496A CN 109301342 A CN109301342 A CN 109301342A
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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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of all-solid-state batteries and preparation method thereof.The preparation method of all-solid-state battery disclosed by the invention is pressed to form all-solid-state battery after being sequentially overlapped positive plate, solid electrolyte film layer, negative electrode tab；Wherein, poly- carbonic acid alkenyl esters are contained in positive plate, solid electrolyte film layer and negative electrode tab.The all-solid-state battery that method produced according to the present invention obtains, without additional pressurizer, it can operate normally.
Description
Technical field
The present invention relates to battery technology fields more particularly to a kind of all-solid-state battery and preparation method thereof.
Background technique
Commercial li-ion battery contains low ignition point liquid state organic electrolyte, is easy to appear leakage, inflammable and explosive etc. and asks safely
Topic, largely limits the application field of liquid lithium ionic cell.And it is stored up as electric car and smart grid etc. are large-scale
Energy device is gradually popularized, and more stringent requirements are proposed for the energy density and security performance to battery.
Compared with commercial li-ion battery, all-solid-state battery replaces liquid state organic electrolyte using inorganic solid electrolyte,
The safety problem of lithium ion battery can preferably be solved.Inorganic solid electrolyte can be good at inhibiting the generation and life of Li dendrite
It is long, to improve the cycle life and security performance of lithium metal battery.In addition, inorganic solid electrolyte electrochemical stability window reaches
It to 5V or more, can be matched with high-voltage anode material, and simplify safety device, mitigate battery weight, be greatly improved
The energy density of battery.All-solid-state battery can also unit superposition series connection, simplify battery case, so that it is close to obtain higher energy
Degree.
Wherein, sulfide solid electrolyte due to ionic conductivity is high, composition variation range is wide, cost of material is lower by
The extensive concern of solid electrolyte as all-solid-state battery.But in the preparation method of existing all-solid-state battery, sulfide is solid
Do not have enough bonding forces between the powder of state electrolyte, anode does not have jail between sulfide solid electrolyte film layer, cathode
Solid binding force, it is therefore desirable to there is pressurizer just and can make solid state battery to keep good ionic conductivity and good appearance
Conservation rate is measured, but due to the presence of pressurizer, the energy density of solid state battery monomer can be made to reduce.
Summary of the invention
(1) technical problems to be solved
It can not achieve the technical issues of controlling oneself pressure to solve the all-solid-state battery of the prior art, the present invention provides a kind of complete
Solid state battery and preparation method thereof realizes the self-holding pressure of all-solid-state battery.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
According to an aspect of the present invention, a kind of preparation method of all-solid-state battery is provided, by positive plate, solid electrolyte
After film layer, negative electrode tab are sequentially overlapped, it is pressed to form all-solid-state battery；Wherein,
Contain poly- carbonic acid alkenyl esters in the positive plate, the solid electrolyte film layer and the negative electrode tab.
A kind of embodiment of method produced according to the present invention further comprises step before the superposition: positive plate,
And/or in negative electrode tab, and/or solid electrolyte film layer poly- carbonic acid alkenyl esters heat resolve.
A kind of embodiment of method produced according to the present invention, the positive plate is by being coated on anode collection for anode sizing agent
Fluid is made after removing solvent；Wherein,
The anode sizing agent includes positive electrode and solvent, includes accounting for the positive electrode gross mass in the positive electrode
1~5% by percentage to the quality poly- carbonic acid alkenyl esters.
A kind of embodiment of method produced according to the present invention, the negative electrode tab is by being coated on cathode collection for negative electrode slurry
Fluid is made after removing solvent；Wherein,
The negative electrode slurry includes negative electrode material and solvent, includes accounting for the negative electrode material gross mass in the negative electrode material
1~3% by percentage to the quality poly- carbonic acid alkenyl esters.
A kind of embodiment of method produced according to the present invention, the solid electrolyte film layer is by by solid state electrolysis chylema
Material is coated on positive plate or negative electrode tab is made, wherein
The solid electrolyte slurry includes solid electrolyte material and solvent, includes accounting in the solid electrolyte material
The poly- carbonic acid alkenyl esters of 3~6% by percentage to the quality of the solid electrolyte material gross mass.
A kind of embodiment of method produced according to the present invention, the poly- carbonic acid alkenyl esters include at least one in following
Kind: poly- ethylene carbonate, polypropylene carbonate, poly- butylene, polycyclohexene.
A kind of embodiment of method produced according to the present invention, the poly- carbonic acid alkenyl esters are polypropylene carbonate, described
The molecular weight of polypropylene carbonate is 100000~500000；
It include sulfide solid electrolyte in the solid electrolyte film layer.
A kind of embodiment of method produced according to the present invention, the heating temperature are 220~250 DEG C, and heating time is
30~60min, so that the polypropylene carbonate is decomposed.
A kind of embodiment of method produced according to the present invention, the pressure of the pressurization are 10~200MPa, pressing time
For 5~30min.
According to another aspect of the present invention, a kind of all-solid-state battery that method produced according to the present invention obtains is provided.
(3) beneficial effect
The preparation method of all-solid-state battery according to the present invention, in a first aspect, containing in positive plate and solid electrolyte film layer
There are poly- carbonic acid alkenyl esters, during heating pressurization, poly- carbonic acid alkenyl esters can decompose, due to point of poly- carbonic acid alkenyl esters
Solution, will form hole in the positive electrode material layer of positive plate；Poly- carbonic acid alkenyl esters in solid electrolyte film layer can also decompose,
After it is decomposed, particles of inorganic material present in solid state electrolysis film layer can be filled in the hole formed to positive electrode material layer, to be formed
The positive electrode material layer of fine and close interlaced extruding infiltration and solid electrolyte membrane bed boundary.
Second aspect contains poly- carbonic acid alkenyl esters in solid electrolyte film layer and negative electrode tab, in the process of heating pressurization
In, poly- carbonic acid alkenyl esters can decompose, and due to the decomposition of poly- carbonic acid alkenyl esters, will form hole in solid electrolyte film layer；It is negative
Poly- carbonic acid alkenyl esters in pole piece can also decompose, after its decomposition, inorganic matter present in the negative electrode material layer of negative electrode tab
Particle can fill in the hole formed to solid-state electrolyte layer, so as to form the negative electrode material of fine and close interlaced extruding infiltration
Layer and solid electrolyte membrane bed boundary.
In conclusion the all-solid-state battery that preparation method according to the present invention obtains, has firm knot between layers
With joint efforts, therefore it does not have to additionally use pressurizer, it can is used alone, realizes self-holding pressure.
The all-solid-state battery that method produced according to the present invention obtains both can be normal without additional pressurizer
Operation, realizes self-holding pressure.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the application can
To be combined with each other.
Below in conjunction with specific embodiment, the present invention will be described in detail.The application is made below in conjunction with specific embodiment
It is described in further detail, these embodiments should not be understood as limiting the application range claimed.In embodiment not
Actual conditions person is indicated, is carried out according to conventional conditions or manufacturer's recommended conditions.Factory is not specified in agents useful for same or instrument
Shang Zhe is the conventional products that can be obtained by commercially available purchase.
According to an aspect of the present invention, a kind of preparation method of all-solid-state battery is provided, by positive plate, solid electrolyte
After film layer, negative electrode tab are sequentially overlapped, it is pressed to form all-solid-state battery；Wherein, in positive plate, solid electrolyte film layer and negative
Contain poly- carbonic acid alkenyl esters in pole piece.
The preparation method of all-solid-state battery according to the present invention, in a first aspect, containing in positive plate and solid electrolyte film layer
There are poly- carbonic acid alkenyl esters, during heating pressurization, poly- carbonic acid alkenyl esters can decompose, due to point of poly- carbonic acid alkenyl esters
Solution, will form hole in the positive electrode material layer of positive plate；Poly- carbonic acid alkenyl esters in solid electrolyte film layer can also decompose,
After it is decomposed, particles of inorganic material present in solid state electrolysis film layer can be filled in the hole formed to positive electrode material layer, to be formed
The positive electrode material layer of fine and close interlaced extruding infiltration and solid electrolyte membrane bed boundary.
Second aspect contains poly- carbonic acid alkenyl esters in solid electrolyte film layer and negative electrode tab, in the process of heating pressurization
In, poly- carbonic acid alkenyl esters can decompose, and due to the decomposition of poly- carbonic acid alkenyl esters, will form hole in solid electrolyte film layer；It is negative
Poly- carbonic acid alkenyl esters in pole piece can also decompose, after its decomposition, inorganic matter present in the negative electrode material layer of negative electrode tab
Particle can fill in the hole formed to solid electrolyte film layer, so as to form the cathode material of fine and close interlaced extruding infiltration
The interface of the bed of material and solid electrolyte film layer.
In conclusion the all-solid-state battery that preparation method according to the present invention obtains, has firm knot between layers
With joint efforts, therefore it does not have to additionally use pressurizer, it can is used alone, realizes self-holding pressure.
A kind of embodiment of method produced according to the present invention further comprises step before superposition: positive plate, and/or
The heat resolve of poly- carbonic acid alkenyl esters in negative electrode tab, and/or solid electrolyte film layer.
Positive plate, solid electrolyte film layer and the negative electrode tab in the present invention, refer both to poly- carbonic acid alkenyl esters and do not carry out
The state of heat resolve.
In the preparation process in accordance with the present invention, heating adds after being sequentially overlapped positive plate, negative electrode tab, solid electrolyte film layer
Before swaging is at all-solid-state battery, i.e., before superposition, it can also partially carry out pyrolysis and eliminate poly- carbonic acid alkenyl esters.Such as it is being superimposed
Before, positive plate has carried out heating and has eliminated poly- carbonic acid alkenyl esters；Or positive plate and solid electrolyte film layer heat eliminate it is poly-
Carbonic acid alkenyl esters；Or negative electrode tab and solid electrolyte film layer heat and eliminate poly- carbonic acid alkenyl esters；Or three heats
Eliminate poly- carbonic acid alkenyl esters；As long as finally having carried out heating pressurized treatments, poly- carbonic acid alkenyl esters are decomposed, can be formed and be controlled oneself
The all-solid-state battery of pressure.It is of course also possible to which the decomposition without poly- carbonic acid alkenyl esters, is directly heated after three is superimposed
Pressurization, makes the poly- carbonic acid alkenyl esters wherein contained while removing.
A kind of embodiment of method produced according to the present invention, positive plate is by being coated on anode collection for anode sizing agent
Body obtains after removing solvent；Wherein,
Anode sizing agent includes positive electrode and solvent, include in positive electrode account for positive electrode gross mass with quality percentage
Than 1~5% poly- carbonic acid alkenyl esters of meter.
Preparation method according to the present invention, wherein containing poly- carbonic acid alkenyl esters in anode sizing agent, on the one hand, it is polymerization
Object, has the property of adhesive, therefore when anode sizing agent is coated on plus plate current-collecting body, slurry can be made firmly to be adhered to collection
The surface of fluid, so that the self-holding pressure for realization all-solid-state battery contributes to a certain extent；On the other hand, poly- carbonic acid alkene
Base ester can be pyrolyzed in its pyrolysis temperature range, can form hole in positive electrode material layer after pyrolysis, so as to be solid-state electricity
Solution matter layer in it is inorganic particle filled come in, form the bed boundary of firm connection.
It include the poly- carbonic acid alkenyl for accounting for 1~5% by percentage to the quality of positive electrode gross mass in positive electrode
On the one hand ester does not have the effect of binder, the hole formed after on the other hand decomposing is too wherein content is very little when less than 1%
It is few, the interface of firm connection cannot be formed；When greater than 5%, it is not easy to decompose completely, and the hole formed is too many, can make anode
The accounting of positive electrode active materials is reduced in material, reduces the performance of positive electrode active materials.When therefore, in 1~5% range, both
It can make the moderate number in the hole to be formed, and not influence the performance of positive electrode active materials.
Preparation method according to the present invention, in the present invention positive electrode include: positive electrode active materials, solid electrolyte,
Polypropylene carbonate and conductive agent.
Wherein, the preferred sulfide of positive electrode active materials (such as titanium disulfide or FeS2), nickle cobalt lithium manganate (NCM) and nickel cobalt aluminium
Sour (NCA) lithium；Further preferred Al2O3NCM, NCA of cladding；LiNbO can also be selected3、Li4Ti5O12And Al2O3Cladding
LiCoO2。
The preferred acetylene black of conductive agent, carbon nanotube, graphene, electrically conductive graphite, conductive carbon black, Ketjen black, in carbon fiber
It is at least one.
The preferred sulfide solid electrolyte of solid electrolyte, preferred pulverulence, solid electrolyte raw material is further
It is preferred that Li2S、P2S5And P, LiI, LiCl, P2S3、P2O5、Al2S3、GeS2、SiS2And SnS2One or more of.
Wherein, positive electrode active materials, solid electrolyte, polypropylene carbonate, conductive agent mass ratio be 70~90:30~
10:1~5:3~6.And poly- carbonic acid alkenyl esters account for the 1%~5% of four gross masses, it is further typical but preferred without limitation
1%, 2%, 3%, 4% and 5%.Anode sizing agent be coated on (such as: aluminium foil) on plus plate current-collecting body with a thickness of 50~300 μm.
In the preparation process, removal solvent can dry, and can also dry, preferably dry.It is molten in selection drying removal
When the temperature of agent, the solvent being preferably only capable of in removal slurry, the temperature without decomposing poly- carbonic acid alkenyl esters.And drying temperature and choosing
The solvent selected is related, and when the solvent such as selected is methyl phenyl ethers anisole, drying temperature is 50~120 DEG C, drying time is 0.5~5h.?
Positive plate is formd in the preparation step, wherein containing poly- carbonic acid alkenyl esters.
A kind of embodiment of method produced according to the present invention, negative electrode tab is by being coated on negative pole currect collecting for negative electrode slurry
Body obtains after removing solvent；Wherein,
Negative electrode slurry includes negative electrode material and solvent, include in negative electrode material account for negative electrode material gross mass with quality percentage
Than 1~3% poly- carbonic acid alkenyl esters of meter.
Preparation method according to the present invention, wherein containing poly- carbonic acid alkenyl esters in negative electrode slurry, on the one hand, it is polymerization
Object, has the property of adhesive, therefore when negative electrode slurry is coated on negative current collector, slurry can be made firmly to be adhered to negative
The surface of pole collector, so that the self-holding pressure for realization all-solid-state battery contributes to a certain extent；On the other hand, poly- carbon
Sour alkenyl esters can be pyrolyzed in its pyrolysis temperature range, hole can be formed in negative electrode material layer after pyrolysis, so as to so that solid
Inorganic particle filled in state electrolyte layer comes in, and forms the contact interface of firm connection.
It include the poly- carbonic acid alkenyl for accounting for 1~3% by percentage to the quality of negative electrode material gross mass in negative electrode material
On the one hand ester does not have the effect of binder, the hole formed after on the other hand decomposing is too wherein content is very little when less than 1%
It is few, the interface of firm connection cannot be formed；When greater than 3%, it is not easy to decompose completely, and the hole formed is too many, can make cathode
The performance accounting of negative electrode active material is reduced in material, reduces the performance of negative electrode active material.Therefore at 1~3%, can make
The hole number of formation is moderate, and does not influence the performance of negative electrode active material.
Negative electrode material includes negative electrode active material, sulfide solid electrolyte and poly- carbonic acid alkenyl esters, the mass ratio of three
It is preferred that 50~80:20~50:1~3, and poly- carbonic acid alkenyl esters account for 1 by percentage to the quality of negative electrode material gross mass~
3%, typical but preferably 1%, 2% and 3% without limitation.The slurry thickness being coated on negative current collector (such as: copper foil) is excellent
Select 50~300 μm.Wherein, the preferred graphite of negative electrode active material, Li4Ti5O12, silicon-carbon.
The preferred sulfide solid electrolyte of solid electrolyte, preferred pulverulence, solid electrolyte raw material is further
It is preferred that Li2S、P2S5And P, LiI, LiCl, P2S3、P2O5、Al2S3、GeS2、SiS2And SnS2One or more of.
In the preparation process, removal solvent can dry, and can also dry, preferably dry.It is molten in selection drying removal
When the temperature of agent, the solvent being preferably only capable of in removal slurry, the temperature without decomposing poly- carbonic acid alkenyl esters.And drying temperature and choosing
The solvent selected is related, and when the solvent such as selected is methyl phenyl ethers anisole, drying temperature is 50~120 DEG C, drying time is 0.5~5h.?
Negative electrode tab is formd in the preparation step, wherein containing poly- carbonic acid alkenyl esters.
A kind of embodiment of method produced according to the present invention, solid electrolyte film layer is by applying solid electrolyte slurry
It is overlying on positive plate or negative electrode tab is made, wherein
Solid electrolyte slurry includes solid electrolyte material and solvent, includes accounting for solid state electrolysis in solid electrolyte material
The poly- carbonic acid alkenyl esters of 3~6% by percentage to the quality of material gross mass.
In the preparation process in accordance with the present invention, solid electrolyte slurry is preferably coated on positive plate or negative electrode tab, dried molten
The solid electrolyte film layer being attached in positive plate or negative electrode tab is prepared after agent.It in this way can be to avoid solid electrolyte membrane layer
It is crushed in transfer process.
In the preparation process in accordance with the present invention, solid electrolyte membrane is either prepared separately and is placed on positive plate or negative electrode tab
On, or slurry is coated on positive plate or negative electrode tab and forms solid electrolyte film layer, it is defined as anode in the present invention
The superposition of the superposition of piece and solid electrolyte film layer or negative electrode tab and solid electrolyte film layer.
In the preparation process in accordance with the present invention, under inert conditions, sulfide solid electrolyte is mixed with polypropylene carbonate
It closes, solubilizer is prepared into slurry, by the surface for being coated on positive plate or negative electrode tab with a thickness of 30~100 μm, obtains after removing solvent
To the positive plate for being compounded with solid electrolyte film layer.
In the preparation process in accordance with the present invention, solid electrolyte film layer can be formed in positive plate, can also be formed in cathode
Piece.
In the preparation process, the solvent in solid electrolyte film layer can be removed, and can not also be removed.When removal solvent
It can dry, can also dry, preferably dry.When the temperature of removal solvent is dried in selection, preferably it is only capable of in removal slurry
Solvent, the temperature without decomposing poly- carbonic acid alkenyl esters.And drying temperature is related with the solvent of selection, the solvent such as selected is benzene first
When ether, drying temperature is 50~120 DEG C, drying time is 0.5~5h.Positive plate and solid-state electricity are formd in the preparation step
The composite layer of plasma membrane layer is solved, poly- carbonic acid alkenyl esters are contained.
A kind of embodiment of method produced according to the present invention, poly- carbonic acid alkenyl esters include at least one of following: poly-
Ethylene carbonate, polypropylene carbonate, poly- butylene, polycyclohexene.
Above-mentioned poly- carbonic acid alkenyl esters all have the effect of binder, are added to anode sizing agent, negative electrode slurry, solid electrolyte
In slurry, the slurry of formation can be such that slurry and clad can be coated is firmly combined together in coating to clad can be coated.Separately
Outside, when heating pressurization using the temperature for being higher than its decomposition temperature, above-mentioned material can also be decomposed, in the positive material of positive plate
Bed of material surface forms hole, makes to make solid electrolyte in the particles filled hole to positive electrode surface in solid electrolyte film layer
Film layer and positive electrode material layer are firmly combined together；It can also make to form hole in solid electrolyte membrane layer, fill out negative electrode material
It is charged in the hole of solid electrolyte film layer formation.
A kind of embodiment of method produced according to the present invention, poly- carbonic acid alkenyl esters are polypropylene carbonate, poly- carbonic acid third
The molecular weight of enester is 100000~500000；It include sulfide solid electrolyte in solid electrolyte film layer.
A kind of embodiment of method produced according to the present invention, heating temperature be 220~250 DEG C, heating time be 30~
60min, so that polypropylene carbonate is decomposed.
Preparation method according to the present invention, when the molecular weight of polypropylene carbonate is 100000~500000, molecular weight
Relatively high, viscosity is larger, on the one hand, can make the solid electrolyte obtained when the polypropylene carbonate amount of addition is less
Film forming, wherein the accounting of sulfide solid electrolyte is opposite to be improved, so that the ionic conductivity of solid electrolyte is improved, and by
Less in its additive amount, fast decoupled is complete when can also enable its heating；On the other hand, the poly- carbonic acid third of addition can be made
The anode sizing agent that enester amount obtains when less has good adhesive property, to allow to preferably be bonded in anode collection
On body, fast decoupled is complete when can also enable its drying.
Wherein, the molecular weight of polypropylene carbonate is typical but without limitation preferably: 100000,150000,180000,
200000、250000、300000、350000、400000、450000、500000。
Preparation method of the invention, polypropylene carbonate decomposition temperature is at 230 DEG C or so, when the molecule of polypropylene carbonate
When amount is 100000~500000, decomposition temperature is within the scope of 220~250 DEG C, and in the temperature range, solid electrolyte is
When sulfide solid electrolyte, during the drying process, not only polypropylene carbonate can be decomposed, formation hole, between inorganic sulphide,
Also a degree of crosslinking can occur, so as to so that positive electrode and sulfide solid electrolyte, sulfide solid electrolyte
Combination between negative electrode material is even closer, to further increase positive electrode material layer, solid electrolyte film layer, cathode
Binding force between material layer, to further improve the self-holding pressure energy power of all-solid-state battery.
Wherein, heating temperature is typically but without limitation preferably 220 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 250
℃。
Heating time typically but 30min, 35min preferred without limitation, 40min, 45min, 50min, 55min,
60min。
A kind of embodiment of method produced according to the present invention, the pressure of pressurization are 10~200MPa, the dwell time is 5~
30min。
Preparation method according to the present invention, after heating pressurization, by the surrounding insulating cement of unencapsulated all-solid-state battery
It seals, is sealed again with aluminum plastic film after being removed from the molds, be prepared into the Soft Roll all-solid-state battery for pressure of controlling oneself.
It in the pressure limit, is more advantageous to form the all-solid-state battery with firm connection power, realizes its pressure of controlling oneself
Performance.
According to another aspect of the present invention, a kind of all-solid-state battery that preparation method of the present invention obtains is provided.
The all-solid-state battery that method produced according to the present invention obtains both can be normal without additional pressurizer
Operation, realizes self-holding pressure.
In order to preferably explain the present invention, in order to understand, below with reference to embodiment, the present invention is described in detail.It needs
Illustrate, embodiment is only used for that the present invention will be described, can't limit claims of the invention
System.
Embodiment 1
(1) preparation of positive plate
Positive plate is obtained after dry out solvent by the way that anode sizing agent is coated on plus plate current-collecting body；Wherein, anode sizing agent includes
Positive electrode and solvent include the poly- carbonic acid third for accounting for 3% by percentage to the quality of positive electrode gross mass in positive electrode
Enester (molecular weight 357000).Wherein, positive electrode includes positive electrode active materials, solid electrolyte, polypropylene carbonate, second
Acetylene black, four mass ratio are 80:15:3:2.Positive electrode active materials are LiNbO3The LiNi coated1/3Co1/3Mn1/3O2, solvent
For methyl phenyl ethers anisole.The slurry being prepared is scratched to plus plate current-collecting body aluminium foil, is scratched with a thickness of 200um, in vacuum oven
Middle drying, drying temperature are 60 DEG C, and time 1h obtains positive plate.
(2) preparation of negative electrode tab
Negative electrode tab is obtained after dry out solvent by the way that negative electrode slurry is coated on negative current collector；Wherein, negative electrode slurry includes
Negative electrode material and solvent (methyl phenyl ethers anisole) include 2% by percentage to the quality for accounting for negative electrode material gross mass in negative electrode material
Polypropylene carbonate.Wherein, in negative electrode material include negative electrode active material, sulfide solid electrolyte, polypropylene carbonate, three
The mass ratio of person is 50:47:3；Wherein, negative electrode active material is graphite, and solvent is methyl phenyl ethers anisole.The slurry being prepared is scratched
It to negative current collector copper foil, dries in a vacuum drying oven, drying temperature is 60 DEG C, drying time 1h.
(4) preparation of electrolyte membrane layer
It is made by the way that solid electrolyte slurry to be coated on anode pole piece.Solid electrolyte slurry includes solid electrolyte
Material and solvent include 4% by percentage to the quality for accounting for solid electrolyte material gross mass in solid electrolyte material
Polypropylene carbonate.
In argon gas glove box, sulfide solid electrolyte is mixed with polypropylene carbonate, using methyl phenyl ethers anisole as solvent system
At slurry.Slurry is applied to anode pole piece surface at room temperature, thickness control is 100 μm.
(5) hot pressing of all-solid-state battery is standby
Positive plate compound in step (4)/solid electrolyte film layer and negative electrode tab are sequentially placed in a mold, first 60
DEG C drying 30min, to dry the solvent in solid state electrolysis film layer, subsequent heat resolve polypropylene carbonate (PPC), temperature is
230 DEG C, then time 30min pressurizes, and pressure 20MPa obtains unencapsulated all-solid-state battery.
The surrounding of unencapsulated all-solid-state battery is sealed with insulating cement, is sealed again with aluminum plastic film after being removed from the molds,
It is prepared into the Soft Roll all-solid-state battery for pressure of controlling oneself.
Embodiment 2
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, contain in positive electrode and accounts for positive material
Expect the polypropylene carbonate of 1% by percentage to the quality of gross mass.
Embodiment 3
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, contain in positive electrode and accounts for positive material
Expect the polypropylene carbonate of 2% by percentage to the quality of gross mass.
Embodiment 4
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, contain in positive electrode and accounts for positive material
Expect the polypropylene carbonate of 4% by percentage to the quality of gross mass.
Embodiment 5
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, contain in positive electrode and accounts for positive material
Expect the polypropylene carbonate of 5% by percentage to the quality of gross mass.
Embodiment 6
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, it include accounting for institute in the negative electrode material
State the polypropylene carbonate of 1% by percentage to the quality of negative electrode material gross mass.
Embodiment 7
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, it include accounting for institute in the negative electrode material
State the polypropylene carbonate of 3% by percentage to the quality of negative electrode material gross mass.
Embodiment 8
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, in solid electrolyte film layer, Gu
It include the polypropylene carbonate for accounting for 3% by percentage to the quality of solid electrolyte material gross mass in state electrolyte.
Embodiment 9
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, in solid electrolyte film layer, Gu
It include the polypropylene carbonate for accounting for 5% by percentage to the quality of solid electrolyte material gross mass in state electrolyte.
Embodiment 10
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, in solid electrolyte film layer, Gu
It include the polypropylene carbonate for accounting for 6% by percentage to the quality of solid electrolyte material gross mass in state electrolyte.
Embodiment 11
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, pyrolysis temperature is 220 DEG C.
Embodiment 12
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, pyrolysis temperature is 240 DEG C.
Embodiment 13
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, pyrolysis temperature is 250 DEG C.
Comparative example 1
(1) by positive electrode active materials LiNbO3The LiNi coated1/3Co1/3Mn1/3O2, solid electrolyte, acetylene black powder
Be mixed with anode composite, take it is a certain amount of be put into mold, the wherein anode in the composition of positive electrode and ratio and embodiment 1
Material is identical, but does not include polypropylene carbonate wherein；
(2) sulfide solid electrolyte powder is tabletted, it is put on mold anode composite；
(3) graphite, solid electrolyte, acetylene black powder are mixed with composite negative pole, take and a certain amount of is put into sulphur in mold
On compound electrolyte layer, wherein the composition of negative electrode material and ratio are identical as the negative electrode material in embodiment 1, but do not include wherein
Polypropylene carbonate；Apply the pressure of 20MPa or more.
Comparative example 2
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, pyrolysis temperature is 100 DEG C.
Comparative example 3
The other conditions of the embodiment and embodiment 1 are all the same, the difference is that, pyrolysis temperature is 160 DEG C.
When having carried out all-solid-state battery obtained in embodiment 1-13 and comparative example 1~3 to have 20MPa pressure and no pressure
The test of open-circuit voltage, in 0.1c, the test result of discharge platform voltage is as shown in table 1: table 1
It can be seen that compared with comparative example 1 according to the result in table 1, the all-solid-state battery of embodiment 1~13 is in no pressure
Under the conditions of when detecting, all have discharge voltage plateau, this illustrates the all-solid-state battery that embodiment 1~13 obtains, and realizes self-holding
The performance of pressure, does not need pressurizer.And when being detected under the conditions of no pressure in comparative example 1, positive and negative electrode and electrolyte membrane layer
It not can be carried out dense contact, lead to Resistance Maximum or open circuit, further result in battery inactive, be unable to normal use.
To sum up, pressure of controlling oneself may be implemented in the all-solid-state battery that preparation method of the present invention is prepared, and functional.
The Comparative result of the result of comparative example 2 and 3 and embodiment 1~13 is found, the excellent degree drop of coulombic efficiency
It is low, this is because PPC therein pyrolysis not exclusively affects the capacity performance of positive electrode active materials, reduces the ion of battery
Conductivity and capacity retention ratio.
The above described is only a preferred embodiment of the present invention, being not the limitation for doing other forms to the present invention, appoint
What those skilled in the art can use the equivalence enforcement that technology contents disclosed above were changed or be modified as equivalent variations
Example.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to the above embodiments
What simple modification, equivalent variations and remodeling, still falls within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of all-solid-state battery, which is characterized in that successively by positive plate, solid electrolyte film layer, negative electrode tab
After superposition, it is pressed to form all-solid-state battery；Wherein,
Contain poly- carbonic acid alkenyl esters in the positive plate, the solid electrolyte film layer and the negative electrode tab.
2. preparation method according to claim 1, which is characterized in that further comprise step before the superposition: anode
The heat resolve of poly- carbonic acid alkenyl esters in piece, and/or negative electrode tab, and/or solid electrolyte film layer.
3. preparation method according to claim 1, which is characterized in that the positive plate is by the way that anode sizing agent to be coated on just
Pole collector is made after removing solvent；Wherein,
The anode sizing agent includes positive electrode and solvent, include in the positive electrode account for the positive electrode gross mass with
The poly- carbonic acid alkenyl esters of the 1~5% of mass percent meter.
4. preparation method according to claim 1, which is characterized in that the negative electrode tab is negative by the way that negative electrode slurry to be coated on
Pole collector is made after removing solvent；Wherein,
The negative electrode slurry includes negative electrode material and solvent, include in the negative electrode material account for the negative electrode material gross mass with
The poly- carbonic acid alkenyl esters of the 1~3% of mass percent meter.
5. preparation method according to claim 1, which is characterized in that
The solid electrolyte film layer is made by the way that solid electrolyte slurry is coated on the positive plate or the negative electrode tab,
In,
The solid electrolyte slurry includes solid electrolyte material and solvent, include in the solid electrolyte material account for it is described
The poly- carbonic acid alkenyl esters of 3~6% by percentage to the quality of solid electrolyte material gross mass.
6. preparation method according to claim 1, which is characterized in that the poly- carbonic acid alkenyl esters include in following at least
It is a kind of: poly- ethylene carbonate, polypropylene carbonate, poly- butylene, polycyclohexene.
7. preparation method according to claim 6, which is characterized in that
The poly- carbonic acid alkenyl esters are polypropylene carbonate, and the molecular weight of the polypropylene carbonate is 100000~500000；
It include sulfide solid electrolyte in the solid electrolyte film layer.
8. preparation method according to claim 7, which is characterized in that the heating temperature is 220~250 DEG C, and the time is
30~60min, so that the polypropylene carbonate is decomposed.
9. preparation method according to claim 1, which is characterized in that the pressure of the pressurization is 10~200MPa, time
For 5~30min.
10. a kind of all-solid-state battery that preparation method any according to claim 1~9 obtains.
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