CN106328992B - A kind of preparation method of lithium ion battery and the lithium ion battery - Google Patents
A kind of preparation method of lithium ion battery and the lithium ion battery Download PDFInfo
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- CN106328992B CN106328992B CN201510371599.4A CN201510371599A CN106328992B CN 106328992 B CN106328992 B CN 106328992B CN 201510371599 A CN201510371599 A CN 201510371599A CN 106328992 B CN106328992 B CN 106328992B
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
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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
- H01M10/058—Construction or manufacture
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention proposes the preparation methods of a kind of lithium ion battery and the lithium ion battery, the lithium ion battery include battery case and be located at the intracorporal battery core of battery case, the battery core includes anode, cathode and the electrolyte between anode and cathode, it is characterized in that, the electrolyte includes the second solid-state electrolyte layer positioned at the first solid-state electrolyte layer of the positive electrode surface and positioned at the negative terminal surface, and first solid-state electrolyte layer is in contact with second solid-state electrolyte layer；First solid-state electrolyte layer includes first binder and the first inorganic electrolyte particle, and the first inorganic electrolyte particle is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；Second solid-state electrolyte layer includes the second binder and the second inorganic electrolyte particle, and the second inorganic electrolyte particle is sulfide-based solid electrolyte.The lithium ion battery being prepared by the present invention, it is not only highly-safe, and capacity with higher and good cycle performance.
Description
Technical field
The invention belongs to field of lithium ion battery more particularly to a kind of lithium ion battery and preparation method thereof.
Background technique
Lithium ion battery is compared with other batteries, and with light weight, small in size, operating voltage is high, energy density is high, output
Power is big, charge efficiency is high, memory-less effect, the advantages that having extended cycle life, and not only obtains in fields such as mobile phone, laptops
It is widely applied, and is also considered as one of electric vehicle, the optimal selection of large-scale energy storage device, at present commercial li-ion electricity
Liquid electrolyte is widely used in pond；But there are volatility and combustibility for organic liquid electrolyte, lead to lithium ion battery always
There are the risks of leakage, burning, explosion, since there are volatility and combustibility, the lithiums of electrolyte system for organic liquid electrolyte
Ion battery cannot be completely eliminated security risk.On the other hand, since there are small molecule solvents in electrolyte, when cathode voltage mistake
There are problems that solvent oxidation decomposition when high, so high pressure, high-energy density positive electrode can not slowly promote and apply, battery
Energy density is difficult to further increase；Especially current energy storage and requirement of the electric automobiles to lithium battery safety are higher, thorough
The safety problem that bottom solves lithium battery seems extremely urgent.The ultimate strategy for eliminating lithium battery security risk is using solid state electrolysis
Matter replaces electrolyte to prepare all-solid-state battery.
Solid lithium battery is divided into all solid-state thin-film lithium battery and accumulation type (bulk-type) solid lithium battery.Quan Gu
State film lithium cell is to prepare anode, electrolyte, cathode respectively using gas-phase deposition, and whole process is needed in high vacuum ring
Molecular level deposition is realized in border, due to higher cost, is only applied only to microelectronic field, and a possibility that large-scale application is smaller.
Accumulation type solid lithium battery mostly uses greatly the laminated sheets such as positive pole powder, electrolyte powder, cathode, and electrolyte is typically chosen sulphur
Compound system solid electrolyte (Thio-LISICON)；It is whole since sulfide-based solid electrolyte encounters air and moisture is unstable
A process needs to complete in an inert atmosphere, and technology difficulty is larger.Currently, such commercialized product there is no to occur, it is in addition high
High cost is also to hinder all solid-state thin-film lithium battery big barrier that further enlargement promotes and applies；Accumulation type (bulk-
Type the problems such as) the sulfide-based solid electrolyte that solid lithium battery uses equally exists higher cost, process operability is poor；
Importantly, there are interfacial effects between sulfide-based solid electrolyte and positive electrode, all-solid-state battery is greatly influenced
Performance.Positive electrode surface cladding is one of the strategy for alleviating the problem, but due to body during electrode material removal lithium embedded
The factors such as product variation often will cause clad rupture etc., so it is neutral that solid lithium battery cyclic process still can not be solved
The problem of capable of deteriorating.
Summary of the invention
The present invention in view of the above technical problems, proposes a kind of lithium ion battery, including battery case and is located at battery
The intracorporal battery core of shell, the battery core include anode, cathode and the electrolyte between anode and cathode, which is characterized in that
The electrolyte includes the second solid-state positioned at the first solid-state electrolyte layer of the positive electrode surface and positioned at the negative terminal surface
Electrolyte layer, first solid-state electrolyte layer are in contact with second solid-state electrolyte layer；First solid electrolyte
Layer includes first binder and the first inorganic electrolyte particle, and the first inorganic electrolyte particle is NASICON type without electromechanics
Solve matter and/or Ca-Ti ore type inorganic electrolyte；Second solid-state electrolyte layer includes the second binder and the second inorganic electrolyte
Matter particle, the second inorganic electrolyte particle are sulfide-based solid electrolyte.
The present invention is by being arranged the first solid-state electrolyte layer in positive electrode surface and the second solid-state electricity being arranged in negative terminal surface
Matter layer is solved, first solid-state electrolyte layer is in contact with second solid-state electrolyte layer；And the first solid-state electrolyte layer packet
First binder and the first inorganic electrolyte particle are included, the first inorganic electrolyte particle is NASICON type inorganic electrolyte
And/or Ca-Ti ore type inorganic electrolyte, second solid-state electrolyte layer include the second binder and the second inorganic electrolyte
Grain, the second inorganic electrolyte particle are sulfide-based solid electrolyte；One side NASICON type inorganic electrolyte and/or
Ca-Ti ore type inorganic electrolyte layer can maintain the ionic conductivity of positive electrode and electrolyte, while can avoid sulfide-based solid-state
The performance of high pressure lithium battery has been effectively ensured in side reaction between electrolyte and high-voltage anode material.Moreover, the hair of the application
Bright people is had found by many experiments, if NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte layer and cathode are direct
Contact is then easy to be restored by the negative electrode material of low potential, electrolyte electronic conductance is caused to increase and cause battery short circuit；The present invention
In, also there is sulfide-based solid between NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte layer and cathode
Electrolyte layer, can effectively avoid NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte layer is gone back under low potential
Original, and the presence of sulfide-based solid electrolyte layer ensure that the normal performance of low potential capacity of negative plates, in addition, double-layer structure
Electrolyte barrier layer each other, can effectively block respectively because of potential problem bring side reaction, guarantee the high voltage and high energy of battery
Metric density is conducive to improve battery safety height and cycle performance.
It is not only highly-safe by the lithium ion battery that is prepared of the present invention, and capacity with higher and good follow
Ring performance.
Present invention further proposes a kind of preparation methods of lithium ion battery, comprising:
(1) anode and cathode are provided, the anode includes plus plate current-collecting body and the anode positioned at plus plate current-collecting body surface
Material, the cathode include negative current collector and the negative electrode material positioned at negative current collector surface；
(2) electrolyte is prepared between the positive electrode and negative electrode, the electrolyte includes being located at the positive electrode surface
The first solid-state electrolyte layer and the second solid-state electrolyte layer positioned at the negative electrode material surface；
(3) the first solid-state electrolyte layer is in contact with the second solid-state electrolyte layer, compression moulding is placed on battery case
Interior encapsulation obtains lithium ion battery.
Lithium ion battery prepared by the present invention can be realized higher energy density, high security and preferable cyclicity
Energy.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
Lithium ion battery provided by the invention, including battery case and be located at the intracorporal battery core of battery case, the battery core
Including anode, cathode and the electrolyte between anode and cathode, the electrolyte includes being located at the positive electrode surface
First solid-state electrolyte layer and the second solid-state electrolyte layer positioned at the negative terminal surface, first solid-state electrolyte layer and institute
The second solid-state electrolyte layer is stated to be in contact；First solid-state electrolyte layer includes first binder and the first inorganic electrolyte
Grain, the first inorganic electrolyte particle are NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；Described
Two solid-state electrolyte layers include the second binder and the second inorganic electrolyte particle, and the second inorganic electrolyte particle is vulcanization
Object system solid electrolyte.
In lithium ion battery of the invention, the anode of lithium ion battery is not particularly limited, can be used existing lithium from
The anode generallyd use in sub- battery；Specifically, it is described anode include plus plate current-collecting body and positioned at plus plate current-collecting body surface just
Pole material.
Wherein, plus plate current-collecting body plus plate current-collecting body known to those skilled in the art, for example, can selected from aluminium foil or
Aluminium foil.
The positive electrode includes positive active material, positive conductive agent and third binder, the positive active material
Selected from LiNi0.5Mn1.5O4、LiMn2O4、LiCoPO4、LiNiPO4、Li3V3(PO4)3、LiMnPO4、LiNi1/3Co1/3Mn1/3O2In
It is one or more；The conduction being used in lithium ion cell positive that the positive conductive agent is known to the skilled person
Agent, specific bottom, the positive conductive agent can be selected from least one of acetylene black, carbon nanotube, HV, carbon black；The third
The binder being used in lithium ion cell positive that binder is known to the skilled person, specifically, the binder can
To be selected from fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber
One of (SBR) or it is a variety of.
There is good interface compatibility between the positive electrode and electrolyte that the present invention selects, be provided simultaneously with higher electricity
Pressure, may be implemented high-energy density.Especially current electrolyte system is unable to satisfy high-voltage anode material demand, leads to liquid
The lithium ion battery of electrolyte system is difficult to further increase its energy density；Solid electrolyte is expected to thoroughly improve the problem.
In above-mentioned positive electrode, the content of positive conductive agent and third binder is known to the skilled person, specifically
Ground, on the basis of the weight of positive active material, the content of conductive agent is 0.1-20wt%, preferably 1-10wt%；Third is viscous
The content for tying agent is 0.01-10wt%, preferably 0.02-5wt%.
In lithium ion battery of the invention, it is preferable that it in the positive electrode further include additive, the additive choosing
From LiNbO3、LiTaO3、Lix1La1/(3-x1)TaO3、Li3PO4、Lix2Tiy2(PO4)3、Lix3Aly3Tiz3(PO4)3、Li2SiO3、
Li2O、Li2S、Li2S-P2S5、Li2S-SiS2-P2S5、Lix4Siy4Sz4、Lix5Py5Sz5、LiBO2、Li3.6Si0.6P0.4O4One of
It is or a variety of, wherein 0 < x1< 3；0 < x22,0 < y of <2< 3；0 < x32,0 < y of <31,0 < z of <3< 3；0 < x43,0 < y of <4
2,0 < z of <4< 4；0 < x53,0 < y of <53,0 < z of <5< 7；The additive-free content is 0.1-50wt%, preferably
0.5-20wt%.
Wettable electrolyte is not present in all-solid-state battery, the ionic conduction between electrode particle can not be by being similar to
The bridge joint of electrolyte, which acts on, to carry out, and the addition of additive can alleviate the technical problem, above-mentioned by adding in positive electrode
Additive, the lithium ion battery being prepared also have better charge-discharge performance and cycle performance.
In lithium ion battery of the invention, the cathode of lithium ion battery is not particularly limited, can be existing lithium ion
The cathode generallyd use in battery；Specifically, the cathode includes negative current collector and positioned at the negative current collector surface
Negative electrode material.
The negative current collector that the negative current collector is known to the skilled person, for example, aluminium foil or copper can be selected from
Foil.
The negative electrode material includes negative electrode active material and the 4th binder；The negative electrode active material can be this field
Conventional negative electrode active material；Specifically, the negative electrode active material is in carbon material, tin alloy, silicon alloy, silicon, tin, germanium
It is one or more；Further, the carbon material can be selected from natural graphite, natural modified graphite, artificial graphite, petroleum
One of burnt, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, tin alloy and silicon alloy are a variety of, preferably artificial graphite and
Natural modified graphite；Meanwhile negative electrode active material may be lithium metal, lithium-indium alloy etc.；In general, according to actual use feelings
Condition can also contain cathode conductive agent in the negative electrode material, and the cathode conductive agent is not particularly limited, and can be ability
The cathode conductive agent of domain routine, such as can be in carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive black and electrically conductive graphite
It is one or more；4th binder is the binder well known in the art in negative electrode of lithium ion battery, specifically
Ground, the 4th binder can be selected from polythiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, gather
Styrene, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, gathers polyacrylamide
Oxireme, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxylic propyl
One of cellulose, ethyl cellulose, sodium carboxymethylcellulose, styrene-butadiene latex are a variety of.
In above-mentioned negative electrode material, the content of negative electrode active material and the 4th binder is known to the skilled person,
Specifically, on the basis of the weight of the negative electrode active material, the content of the cathode conductive agent is 0.5-10wt%；Described
The content of four binders is 0.01-10wt%.
Lithium ion battery provided by the invention further includes electrolyte between the positive electrode and negative electrode, which is characterized in that institute
Stating electrolyte includes the first solid-state electrolyte layer positioned at the positive electrode surface and the second solid-state electricity positioned at the negative terminal surface
Matter layer is solved, first solid-state electrolyte layer is in contact with second solid-state electrolyte layer；First solid-state electrolyte layer
Including first binder and the first inorganic electrolyte particle, the first inorganic electrolyte particle is NASICON type inorganic electrolyte
Matter and/or Ca-Ti ore type inorganic electrolyte；Second solid-state electrolyte layer includes the second binder and the second inorganic electrolyte
Particle, the second inorganic electrolyte particle are sulfide-based solid electrolyte.
Lithium ion battery provided by the invention, wherein the sulfide-based solid electrolyte is the Li of glassy state2S-P2S5、
The Li of crystalline stateX 'MY 'PSZ 'Or the Li of glass ceramics state2S-P2S5One of or it is a variety of, wherein M is one of Si, Ge, Sn
Or a variety of, '≤1 x '+4y+5=2z of ' ', 0≤y；Wherein Li2S-P2S5Refer to the Li prepared according to a certain percentage2S and P2S5
Compound；Preferably, in preparation Li2S-P2S5When compound, the Li2S and P2S5Between molar ratio be 60:40~90:
10。
The lithium ion battery proposed according to the present invention, the Li of the glassy state2S-P2S5The preferably Li of glassy state7P3S11、
The 70Li of glassy state2S-30P2S5One or both of.
In the present invention, the Li of glassy state2S-P2S5Refer to Li2S-P2S5In glassy state, the Li of crystalline stateX 'MY 'PSzRefer to
LiX 'MY 'PSzIn crystalline state, the Li of glass ceramics state2S-P2S5Refer to Li2S-P2S5In glass ceramics state, glass state
Li7P3S11Refer to Li7P3S11In glassy state, the 70Li of glassy state2S-30P2S5Refer to 70Li2S-30P2S5In glassy state.
Lithium ion battery provided by the invention, wherein the NASICON type inorganic electrolyte is LiM2(PO4)3And its doping
One of object is a variety of, wherein M is selected from Ti, Zr, Ge, Sn or Pb, the doped chemical in the dopant be selected from Mg, Ca,
One of Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V or a variety of；
The Ca-Ti ore type inorganic electrolyte has following composition: AxByTiO3、AxByTa2O6、AxByNb2O6Or
AhMkDnTiwO3；Wherein x+3y=2, h+2k+5n+4w=6,0 < x <, 2,0 < y < 2/3, h, k, n, w are all larger than 0；A is selected from Li, Na
One of element is a variety of, and B is selected from one of La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element or a variety of, M be selected from Sr,
One of Ca, Ba, Ir, Pt element is a variety of, and D is selected from one of Nb, Ta element or a variety of.
The lithium ion battery proposed according to the present invention, it is further preferred that above-mentioned first solid-state electrolyte layer with a thickness of
1-50 μm, above-mentioned second solid-state electrolyte layer with a thickness of 1-50 μm；By the first solid-state electrolyte layer and the second solid electrolyte
Thickness thus is arranged in layer, on the one hand can prevent the electronic conduction between positive and negative anodes, prevent short circuit；On the other hand it can maintain just
Ionic conduction between cathode guarantees the energy output of battery.
The lithium ion battery provided according to the present invention, it is further preferred that in the first solid-state electrolyte layer, with described
On the basis of the total weight of one solid-state electrolyte layer, the content of the first inorganic electrolyte particle is 80%-99.5%；It is solid second
In state electrolyte layer, on the basis of the total weight of second solid-state electrolyte layer, the second inorganic electrolyte particle contains
Amount is 80%-99.5%.
The lithium ion battery provided according to the present invention, further, in first solid-state electrolyte layer, with described
On the basis of the total weight of one solid-state electrolyte layer, the content of the first binder is 0.5%-20%；In the second solid-state electricity
It solves in matter layer, on the basis of the total weight of second solid-state electrolyte layer, the content of second binder is 0.5%-20%.
Further, the first binder, the second binder are independently selected from polythiophene, polypyrrole, poly- four
Vinyl fluoride, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, benzene
Ethylene-butylene rubber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin, acrylic resin,
Phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethylcellulose,
One of styrene-butadiene latex is a variety of.
Invention further provides a kind of preparation methods of lithium ion battery, comprising:
(1) anode and cathode are provided, the anode includes plus plate current-collecting body and the anode positioned at plus plate current-collecting body surface
Material, the cathode include negative current collector and the negative electrode material positioned at negative current collector surface；
(2) electrolyte is prepared between the positive electrode and negative electrode, the electrolyte includes being located at the positive electrode surface
The first solid-state electrolyte layer and the second solid-state electrolyte layer positioned at the negative electrode material surface；
(3) the first solid-state electrolyte layer is in contact with the second solid-state electrolyte layer, compression moulding is placed on battery case
Interior encapsulation obtains lithium ion battery.
The preparation method of the lithium ion battery proposed according to the present invention, which is characterized in that this method further comprises: in institute
The surface for stating positive electrode prepares the first solid-state electrolyte layer；The second solid-state is prepared on the surface of first solid-state electrolyte layer
Electrolyte layer；The cathode is placed in the surface of second solid-state electrolyte layer, compression moulding.
The preparation method of the lithium ion battery proposed according to the present invention, which is characterized in that first solid-state electrolyte layer
Including first binder and the first inorganic electrolyte particle, the first inorganic electrolyte particle is NASICON type inorganic electrolyte
Matter and/or Ca-Ti ore type inorganic electrolyte；Second solid-state electrolyte layer includes the second binder and the second inorganic electrolyte
Particle, the second inorganic electrolyte particle are sulfide-based solid electrolyte.
The preparation method of the lithium ion battery proposed according to the present invention, it is further preferred that in the table of the positive electrode
Wheat flour includes: to coat the first solid electrolyte slurry on the surface of the positive electrode for the method for the first solid-state electrolyte layer,
Then it is dried at 50-200 DEG C, tabletting, forms first solid-state electrolyte layer on the positive electrode surface, obtain anode
With the complex of the first solid-state electrolyte layer；Wherein, the first solid electrolyte slurry includes by first binder, the first nothing
Machine electrolyte granular and the first solvent are mixed to get, and the first inorganic electrolyte particle is NASICON type inorganic electrolyte
And/or Ca-Ti ore type inorganic electrolyte；On the basis of the total weight of the first solid electrolyte slurry, the first binder
Content be 0.5%-20%, the content of first solvent is 20%-350%；Wherein, first binder is selected from polythiophene, poly- pyrrole
It coughs up, the copolymerization of polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene
Resin, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin, propylene
Acid resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, carboxymethyl are fine
Tie up one of plain sodium (CMC), styrene-butadiene latex (SBR) or a variety of；First solvent is selected from N-Methyl pyrrolidone, water, ethyl alcohol, third
One or more of ketone；The first solid-state electrolyte layer, the first solid state electrolysis being prepared are prepared on the surface of positive electrode
Matter layer with a thickness of 1-50 μm.
The lithium ion battery proposed according to the present invention, it is further preferred that on the surface of first solid-state electrolyte layer
The method for preparing the second solid-state electrolyte layer includes: to coat the second solid-state on the surface of the first solid-state electrolyte layer in glove box
Then electrolyte slurry is dried, tabletting at 50-200 DEG C, form described second on the surface of first solid-state electrolyte layer
Solid-state electrolyte layer obtains the complex of anode, the first solid-state electrolyte layer, the second solid-state electrolyte layer three-decker；Wherein,
The second solid electrolyte slurry includes being mixed to get the second binder, the second inorganic electrolyte particle and the second solvent；
The second inorganic electrolyte particle is sulfide-based solid electrolyte；Total weight with the second solid electrolyte slurry is
Benchmark, the content of second binder are 0.5%-20%, and the content of second solvent is 20%-350%, wherein second is viscous
It ties agent and is selected from polythiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide
Amine, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyethylene
Pyrrolidones, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose
One of element, polyethylene glycol oxide, sodium carboxymethylcellulose (CMC), styrene-butadiene latex (SBR) are a variety of；Second solvent is selected from N-
One or more of methyl pyrrolidone, water, ethyl alcohol, acetone；The second solid-state electrolyte layer being prepared with a thickness of 1-
50μm。
Above-mentioned anode can be prepared by purchase or voluntarily, and positive preparation method is known to the skilled person, such as
Anode sizing agent is coated on plus plate current-collecting body, anode is prepared through drying, calendering；Wherein, anode sizing agent includes that anode is living
Property substance, positive conductive agent, third binder and positive solvent be mixed to get, wherein positive active material, positive conductive agent,
Third binder and its content as it was noted above, repeat no more again；By positive active material, positive conductive agent, third bonding
Agent and positive solvent are mixed to get anode sizing agent, and then anode sizing agent is coated on plus plate current-collecting body and is dried, was dried
Cheng Zhong, positive solvent volatilization are removed, and substance used by the anode solvent and the amount of addition are those skilled in the art institute
It is known, it repeats no more again.
Preferably, in the preparation process of above-mentioned anode, inorganic solid electrolyte addition can be also added in anode sizing agent
Agent, the inorganic solid electrolyte additive are selected from LiNbO3、LiTaO3、Lix1La1/(3-x1)TaO3、Li3PO4、Lix2Tiy2
(PO4)3、Lix3Aly3Tiz3(PO4)3、Li2SiO3、Li2O、Li2S、Li2S-P2S5、Li2S-SiS2-P2S5、Lix4Siy4Sz4、
Lix5Py5Sz5、LiBO2、Li3.6Si0.6P0.4O4One of or it is a variety of, wherein 0 < x1< 3；0 < x22,0 < y of <2< 3；0 <
x32,0 < y of <31,0 < z of <3< 3；0 < x43,0 < y of <42,0 < z of <4< 4；0 < x53,0 < y of <53,0 < z of <5< 7；Institute
The content for stating inorganic solid electrolyte additive is 0.1-50wt%, preferably 0.5-20wt%.
After anode is prepared, the first solid-state electrolyte layer is prepared on the surface of positive electrode, is prepared on the surface of anode
After first solid-state electrolyte layer, the second solid-state electrolyte layer is prepared on the surface of first solid-state electrolyte layer；Cathode is provided,
Cathode is placed in the surface of second solid-state electrolyte layer, after compression moulding, encapsulation in battery case is placed in and obtains the present invention
Lithium ion battery.
The cathode can be prepared by purchase or voluntarily, the preparation that the preparation method of cathode is known to the skilled person
Method, such as negative electrode slurry is coated on negative current collector, cathode is prepared through drying, calendering；Wherein, negative electrode slurry packet
It includes and is mixed to get negative electrode active material, the 4th binder and cathode solvent, wherein negative electrode active material and the 4th binder
Specific substance classes and its content are as previously mentioned, details are not described herein；Preferably, it can also be added in the negative electrode slurry negative
Pole conductive agent, the content of the cathode conductive agent are 0.5-10wt%；By negative electrode active material, the 4th binder and cathode solvent
It is mixed to get negative electrode slurry, then negative electrode slurry is coated on negative current collector and is dried, in drying course, cathode solvent
Volatilization is removed, and substance used by the cathode solvent and the amount of addition are known to those skilled in the art, again no longer
It repeats.
Cathode is placed in the second solid-state in the above-mentioned methods by the preparation method of the lithium ion battery provided according to the present invention
The surface of electrolyte layer, compression moulding are placed on encapsulation in battery case and obtain lithium ion battery, and the packaging method is this
The packaging method of battery well known to the technical staff of field, details are not described herein.
According to the preparation method for the lithium ion battery that invention provides, in above-mentioned steps (3), the side of the compression moulding
Method are as follows: the hot pressing 0.05-10h at 50-300 DEG C, 0.1-50MPa.
In the application, lithium ion battery can also be prepared: being provided anode, coated above-mentioned first on positive electrode surface
Then solid electrolyte slurry is dried, tabletting at 50-200 DEG C, form the first solid-state electricity on the positive electrode surface
Solve matter layer；Cathode is provided, above-mentioned second solid electrolyte slurry is coated on negative electrode material surface, is then dried at 50-200 DEG C
Dry, tabletting forms second solid-state electrolyte layer on the surface of the negative electrode material；Then by the first solid-state electrolyte layer with
The contact of second solid-state electrolyte layer, compression moulding obtain lithium ion battery.
The present invention is described in more detail by the following examples.
Embodiment 1
The preparation of anode:
By 930 grams of positive electrode active materials LiNi0.5Mn1.5O4(93%), 30 grams of bonding agent PVDF(3%), 20 grams of acetylene blacks
(2%), 20g conductive agent HV(2%) it is added to 1500 grams of solvent NMP(N-methyl pyrrolidones) in, then in de-airing mixer
Stirring, forms the anode sizing agent of stable uniform.The anode sizing agent is equably intermittently coated on to aluminium foil (aluminium foil size are as follows: width
160 millimeters, 16 microns of thickness) two sides on, then 120 DEG C of drying, obtain anode after roll squeezer tabletting；
The preparation of first solid electrolyte:
By 950 grams of inorganic solid electrolyte material Li1.3Al0.3Ti1.7(PO4)3(95%), 5 grams of binder SBR(5%)
It is added in 1000 grams of deionized waters, is then stirred in de-airing mixer, form the first solid state electrolysis chylema of stable uniform
The first solid electrolyte slurry is continuously coated on the surface of the positive electrode for the anode that step 1 obtains by material, and then 120
DEG C drying, by roll squeezer tabletting, the first solid-state electrolyte layer is formed on anode；Wherein, the thickness of the first solid-state electrolyte layer
Degree is 40 μm；
The preparation of second solid-state electrolyte layer:
In glove box, by the 70Li of 600 grams of glassy state2S-30P2S5It is added in 1200 grams of toluene solution, wherein first
Contain 30g butadiene rubber binder in benzole soln, then heating stirring obtains the second solid electrolyte slurry, this second is consolidated
State electrolyte slurry is continuously coated on the surface of above-mentioned first solid electrolyte, and then 60 DEG C of drying, cut out as 485(long) × 46
The size of (width)；Wherein, the second solid-state electrolyte layer with a thickness of 20 μm；
The preparation of cathode:
By 940 grams of negative electrode active material artificial graphites (94%), 30 grams of bonding agent CMC(3%) and 30 grams of bonding agent SBR(3%)
It is added in 1200 grams of deionized waters, is then stirred in de-airing mixer, form the negative electrode slurry of stable uniform, by the cathode
Slurry is equably intermittently coated on the two sides of copper foil (aluminium foil size are as follows: 160 millimeters of width, 16 microns of thickness), and then 120 DEG C
Drying, after roll squeezer tabletting, cuts out as the negative electrode tab of 480(long) × 45(wide) size；
Above-mentioned negative electrode tab is placed in the surface of the second solid electrolyte in glove box, and alignment is placed on hot press after cutting out
In, carry out 150 DEG C of hot pressing 1 hour, be honored as a queen using aluminum plastic film vacuum-pumping density, take out sample, in isostatic pressing machine by 200MPa,
Up to the lithium ion battery S1 of the present embodiment after 300S compacting.
Embodiment 2
Lithium ion battery is prepared using method same as Example 1, the difference is that, prepare the first solid electrolyte
During layer, Li is used0.5La0.5TiO3Replace the Li in embodiment 11.3Al0.3Ti1.7(PO4)3, other with 1 phase of embodiment
Together, lithium ion battery S2 is prepared.
Embodiment 3
Lithium ion battery is prepared using method same as Example 1, the difference is that, prepare the second solid electrolyte
During layer, 80Li is used2S-20P2S5Glass ceramics replaces the 70Li of the glassy state in embodiment 12S-30P2S5, it is prepared
Lithium ion battery S3.
Embodiment 4
Lithium ion battery is prepared using method same as Example 1, the difference is that, prepare the first solid electrolyte
During layer, Li is used0.35La0.55TiO3Replace the Li in embodiment 11.3Al0.3Ti1.7(PO4)3, lithium ion battery is prepared
S4。
Embodiment 5
Lithium ion battery is prepared using method same as Example 1, the difference is that, prepare the second solid electrolyte
During layer, with the Li of crystalline state10SnP2S12Replace the 70Li of the glassy state in embodiment 12S-30P2S5, be prepared lithium from
Sub- battery S5.
Embodiment 6
Lithium ion battery is prepared using method same as Example 1, the difference is that, during preparation anode,
Positive active material LiNiPO4Replace LiNi0.5Mn1.5O4, lithium ion battery S6 is prepared.
Embodiment 7
Lithium ion battery is prepared using method same as Example 1, the difference is that, first electrolyte layer
With a thickness of 15 μm, second electrolyte layer with a thickness of 10 μm, lithium ion battery S7 is prepared.
Embodiment 8
Lithium ion battery is prepared using method same as Example 1, the difference is that, first electrolyte layer
With a thickness of 5 μm, second electrolyte layer with a thickness of 35 μm, lithium ion battery S8 is prepared.
Comparative example 1
Anode same as Example 1, cathode and the polypropylene diaphragm with a thickness of 20 μm are wound into rectangular lithium ion electricity
The battery core in pond, then up to lithium ion battery DS1 after fluid injection, sealing, ageing, chemical conversion, partial volume.
Comparative example 2
Preparation method is substantially the same manner as Example 1, the difference is that, the first solid-state electrolyte layer is not prepared, is directly existed
The surface of positive or negative pole prepares the second solid-state electrolyte layer, obtains lithium ion battery DS2.
Comparative example 3
Preparation method is substantially the same manner as Example 1, the difference is that, the second solid-state electrolyte layer is not prepared, is directly existed
The surface of positive or negative pole prepares the first solid-state electrolyte layer, obtains lithium ion battery DS3.
Performance test
The battery that each embodiment and comparative example is prepared respectively is taken 20, in LAND CT 2001C secondary cell performance
In detection device, under the conditions of 25 ± 1 DEG C, battery is subjected to charge and discharge cycles test with 0.0.1C.Steps are as follows: shelving 10min；
Constant-voltage charge to 5V/0.05C end；Shelve 10min；Constant-current discharge is to 3.0V, as 1 time circulation.The step is repeated, is circulated throughout
In journey when battery capacity 80% lower than discharge capacity for the first time, loop termination, the cycle-index is the cycle life of battery,
Every group is averaged.
Test result is as follows:
Circulating battery 650 times of the preparation of embodiment 1；
Circulating battery 532 times of the preparation of embodiment 2；
Circulating battery 634 times of the preparation of embodiment 3；
Circulating battery 628 times of the preparation of embodiment 4；
Circulating battery 438 times of the preparation of embodiment 5；
Circulating battery 395 times of the preparation of embodiment 6；
Circulating battery 682 times of the preparation of embodiment 7；
Circulating battery 352 times of the preparation of embodiment 8；
For circulating battery prepared by comparative example 1 less than 5 times, percentage of batteries persistently produces gas to battery swell in cyclic process,
And then it catches fire；
Short circuit occurs during battery initial charge prepared by comparative example 2, voltage continuous decrease is zero, can not be followed
Ring；
Circulating battery 35 times of the preparation of comparative example 3.
By above-mentioned test: all solid state high voltage lithium battery electric core provided by the invention have excellent cycle performance and
Security performance, a series of security performances that can effectively avoid liquid electrolyte from causing and one-component inorganic solid electrolyte circulation
The problem of performance difference.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (14)
1. a kind of lithium ion battery, including battery case and it is located at the intracorporal battery core of battery case, the battery core includes anode, negative
Pole and the electrolyte between anode and cathode, which is characterized in that the electrolyte includes being located at the positive electrode surface
First solid-state electrolyte layer and the second solid-state electrolyte layer positioned at the negative terminal surface, first solid-state electrolyte layer and institute
The second solid-state electrolyte layer is stated to be in contact；First solid-state electrolyte layer is by including first binder and the first inorganic electrolyte
First solid electrolyte slurry of particle coats to be formed, and the first inorganic electrolyte particle is NASICON type inorganic electrolyte
And/or Ca-Ti ore type inorganic electrolyte；Second solid-state electrolyte layer is by including the second binder and the second inorganic electrolyte
Second solid electrolyte slurry of particle coats to be formed, and the second inorganic electrolyte particle is sulfide-based solid electrolyte；
First solid-state electrolyte layer with a thickness of 1-50 μm, second solid-state electrolyte layer with a thickness of 1-50 μm.
2. lithium ion battery according to claim 1, which is characterized in that the sulfide-based solid electrolyte is glassy state
Li2S-P2S5, crystalline state LiX 'MY 'PSZ 'Or the Li of glass ceramics state2S-P2S5One of or it is a variety of, wherein M be Si,
One of Ge, Sn or a variety of, '≤1 x '+4y+5=2z of ' ', 0≤y.
3. lithium ion battery according to claim 2, which is characterized in that the Li of the glassy state2S-P2S5Including glassy state
Li7P3S11, glassy state 70Li2S-30P2S5One or both of.
4. lithium ion battery according to claim 1, which is characterized in that the NASICON type inorganic electrolyte is LiM2
(PO4)3And its one of dopant or a variety of, wherein M is selected from Ti, Zr, Ge, Sn or Pb, the doping member in the dopant
Element is selected from one of Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V or a variety of；
The Ca-Ti ore type inorganic electrolyte has following composition: AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3；
Wherein x+3y=2, h+2k+5n+4w=6,0 < x <, 2,0 < y < 2/3, h, k, n, w are all larger than 0；A in Li, Na element one
Kind is a variety of, and B is selected from one of La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element or a variety of, and M is selected from Sr, Ca, Ba, Ir, Pt
One of element is a variety of, and D is selected from one of Nb, Ta element or a variety of.
5. lithium ion battery according to claim 1, which is characterized in that in the first solid-state electrolyte layer, with described
On the basis of the total weight of one solid-state electrolyte layer, the content of the first inorganic electrolyte particle is 80%-99.5%；It is solid second
In state electrolyte layer, on the basis of the total weight of second solid-state electrolyte layer, the second inorganic electrolyte particle contains
Amount is 80%-99.5%.
6. lithium ion battery according to claim 1, which is characterized in that in the first solid-state electrolyte layer, with described
On the basis of the total weight of one solid-state electrolyte layer, the content of the first binder is 0.5%-20%；In the second solid electrolyte
In layer, on the basis of the total weight of second solid-state electrolyte layer, the content of second binder is 0.5%-20%.
7. lithium ion battery according to claim 1, which is characterized in that the first binder, the second binder difference
It is independent to be selected from polythiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide
Amine, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyethylene
Pyrrolidones, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose
One of element, polyethylene glycol oxide, sodium carboxymethylcellulose, styrene-butadiene latex are a variety of.
8. lithium ion battery described in -7 any one according to claim 1, which is characterized in that the anode includes anode collection
Body and the positive electrode on plus plate current-collecting body, the positive electrode include positive active material, the positive active material
Selected from LiNi0.5Mn1.5O4、LiMn2O4、LiCoPO4、LiNiPO4、Li3V3(PO4)3 、LiMnPO4、LiNi1/3Co1/3Mn1/3O2In
It is one or more.
9. lithium ion battery according to claim 7, which is characterized in that it further include additive in the positive electrode, institute
It states additive and is selected from LiNbO3、LiTaO3、Lix1La1/(3-x1)TaO3、Li3PO4、Lix2Tiy2(PO4)3、Lix3Aly3Tiz3(PO4)3、
Li2SiO3、Li2O、Li2S、Li2S-P2S5、Li2S-SiS2-P2S5、Lix4Siy4Sz4、Lix5Py5Sz5、LiBO2、Li3.6Si0.6P0.4O4
One of or it is a variety of, wherein 0 < x1< 3；0 < x22,0 < y of <2< 3；0 < x32,0 < y of <31,0 < z of <3< 3；0 < x4
3,0 < y of <42,0 < z of <4< 4；0 < x53,0 < y of <53,0 < z of <5< 7.
10. a kind of preparation method of lithium ion battery, comprising:
(1) anode and cathode are provided, the anode includes plus plate current-collecting body and the positive electrode positioned at plus plate current-collecting body surface, institute
Stating cathode includes negative current collector and the negative electrode material positioned at negative current collector surface；
(2) electrolyte is prepared between the positive electrode and negative electrode, the electrolyte includes positioned at the of the positive electrode surface
One solid-state electrolyte layer and the second solid-state electrolyte layer positioned at the negative electrode material surface；
(3) the first solid-state electrolyte layer is in contact with the second solid-state electrolyte layer, compression moulding is placed on envelope in battery case
Dress obtains lithium ion battery；
Wherein, first solid-state electrolyte layer is by the first solid-state electricity including first binder and the first inorganic electrolyte particle
Solution chylema material coats to be formed, and the first inorganic electrolyte particle is that NASICON type inorganic electrolyte and/or Ca-Ti ore type are inorganic
Electrolyte；Second solid-state electrolyte layer is by the first solid state electrolysis including the second binder and the second inorganic electrolyte particle
Chylema material coats to be formed, and the second inorganic electrolyte particle is sulfide-based solid electrolyte, first solid electrolyte
Layer with a thickness of 1-50 μm, second solid-state electrolyte layer with a thickness of 1-50 μm.
11. the preparation method of lithium ion battery according to claim 10 characterized by comprising in the positive material
The surface of material prepares the first solid-state electrolyte layer；The second solid electrolyte is prepared on the surface of first solid-state electrolyte layer
Layer；The cathode is placed in the surface of second solid-state electrolyte layer, compression moulding.
12. the preparation method of lithium ion battery according to claim 11, which is characterized in that in the table of the positive electrode
Wheat flour includes: to coat the first solid electrolyte slurry on the surface of the positive electrode for the method for the first solid-state electrolyte layer,
Then it is dried at 50-200 DEG C, tabletting, forms first solid-state electrolyte layer on the positive electrode surface；Described first
Solid electrolyte slurry includes first binder, the first inorganic electrolyte particle and the first solvent.
13. the preparation method of lithium ion battery described in 1 or 12 any one according to claim 1, which is characterized in that described
The method that the surface of first solid-state electrolyte layer prepares the second solid-state electrolyte layer includes: in glove box in the first solid state electrolysis
The surface of matter layer coats the second solid electrolyte slurry, then dries at 50-200 DEG C, tabletting, in first solid state electrolysis
The surface of matter layer forms second solid-state electrolyte layer；The second solid electrolyte slurry includes the second binder, second
Inorganic electrolyte particle and the second solvent.
14. the preparation method of lithium ion battery according to claim 13, which is characterized in that first solvent, second
Solvent is independently selected from one or more of N-Methyl pyrrolidone, water, ethyl alcohol, acetone, toluene, dimethylbenzene, heptane.
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| JP6996244B2 (en) * | 2017-11-15 | 2022-01-17 | トヨタ自動車株式会社 | Manufacturing method of all-solid-state battery, all-solid-state battery and slurry |
| CN109935897B (en) * | 2017-12-19 | 2021-11-26 | 成都大超科技有限公司 | Solid electrolyte, lithium battery cell and lithium battery |
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| CN109935892A (en) * | 2017-12-19 | 2019-06-25 | 成都英诺科技咨询有限公司 | Solid electrolyte and its lithium battery electric core, lithium battery |
| CN108232287B (en) * | 2018-01-25 | 2020-07-03 | 成都特隆美储能技术有限公司 | Lithium ion battery pole piece, manufacturing method and battery cell |
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| CN108428856B (en) * | 2018-03-30 | 2023-10-31 | 苏州清陶新能源科技有限公司 | All-solid-state lithium ion battery interface hot pressing improving process |
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| JP7110943B2 (en) * | 2018-11-28 | 2022-08-02 | トヨタ自動車株式会社 | Method for manufacturing electrode laminate |
| CN111370751B (en) * | 2018-12-25 | 2021-12-07 | 深圳市比亚迪锂电池有限公司 | Solid-state battery, preparation method thereof and electric automobile |
| CN109818053A (en) * | 2019-01-23 | 2019-05-28 | 蜂巢能源科技有限公司 | Composite solid electrolyte film and its preparation method and application |
| CN112310340A (en) * | 2019-07-29 | 2021-02-02 | 通用汽车环球科技运作有限责任公司 | Micron-sized secondary particles with enhanced ionic conductivity for solid state electrodes |
| CN110311167A (en) * | 2019-08-14 | 2019-10-08 | 中国科学院宁波材料技术与工程研究所 | A kind of composite solid electrolyte piece and preparation method thereof and solid state battery |
| CN111009683B (en) * | 2019-11-12 | 2021-11-23 | 北京泰丰先行新能源科技有限公司 | Asymmetric semi-solid electrolyte, preparation method and metal lithium secondary battery |
| CN111430789B (en) * | 2019-11-29 | 2022-09-20 | 蜂巢能源科技有限公司 | Method for reducing porosity of solid electrolyte layer and application thereof |
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