CN108511786A - A kind of solid lithium battery and preparation method thereof - Google Patents

A kind of solid lithium battery and preparation method thereof Download PDF

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Publication number
CN108511786A
CN108511786A CN201710111544.9A CN201710111544A CN108511786A CN 108511786 A CN108511786 A CN 108511786A CN 201710111544 A CN201710111544 A CN 201710111544A CN 108511786 A CN108511786 A CN 108511786A
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solid
lithium
state
positive
lithium battery
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CN108511786B (en
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历彪
郭姿珠
宋威
易观贵
谢静
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BYD Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • General Chemical & Material Sciences (AREA)
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Abstract

This disclosure relates to a kind of solid lithium battery and preparation method thereof, the solid lithium battery includes positive plate, negative plate and solid-state electrolyte layer, the positive plate includes positive active material, and the positive active material includes positive electrode particle and is coated on the fluorine-containing metatitanic acid lithium layer of the positive electrode particle surface.What the disclosure proposed carries out reaction using positive electrode and titanium tetrafluoride, lithium salts mixed sintering and prepares the method that positive electrode surface is coated with the positive active material of fluorine-containing metatitanic acid lithium layer, the surface of positive electrode can equably be modified, obtain surface fluorine content and the controllable positive electrode of fluorine-containing lithium titanate layer thickness, it can stablize clad structure when the positive electrode is used for solid lithium battery, it avoids that interfacial reaction or elements diffusion occur between positive electrode and solid electrolyte, reduces interface impedance.

Description

A kind of solid lithium battery and preparation method thereof
Technical field
This disclosure relates to solid state lithium battery field, and in particular, to a kind of solid lithium battery and preparation method thereof.
Background technology
Solid lithium battery is due to that can occur serious interfacial effect and on boundary between positive electrode and solid electrolyte The elements diffusion problem that face occurs causes the interface impedance between anode and solid electrolyte to greatly increase, to largely effect on The performance of battery, in the prior art generally use surface coated method carried out to positive electrode ask to solve above-mentioned technology Topic, wherein coating is usually oxide, the transition metal oxide containing lithium or fluoride etc..Positive electrode is usually selected LiNbO3、LiTaO3、Li4Ti5O12、Al2O3、BaF2Or CaF2Deng wherein with to LiNbO3Surface coated positive electrode is carried out to answer With the most extensively.
Under normal conditions, binary or ternary oxide material can be used（Such as LiNbO3）Carry out the surface packet of positive electrode It covers, but since oxygen atom and clad structure and can be insufficient to steady with the sulphur atom phase counterdiffusion in existing sulphur system electrolyte It is fixed, cause the interface impedance between positive electrode and electrolyte to reduce unobvious, or gradual in the meeting of charge and discharge process middle impedance Increase, hinders also reduce the service life while charge and discharge process.
Invention content
Purpose of this disclosure is to provide a kind of solid lithium battery and preparation method thereof, the solid lithium battery and preparation side Method can solve the interface impedance between anode and solid electrolyte in the prior art, and element mutually expands greatly and in cyclic process Scattered problem.
To achieve the goals above, the disclosure provides a kind of solid lithium battery, including positive plate, negative plate and solid-state electricity Matter layer is solved, the positive plate includes positive active material, and the positive active material includes positive electrode particle and is coated on institute State the fluorine-containing metatitanic acid lithium layer of positive electrode particle surface.
The disclosure also provides a kind of method preparing solid lithium battery, and the solid lithium battery includes positive plate, bears Pole piece and solid-state electrolyte layer, this method comprises the following steps：
（1）Titanium tetrafluoride is added into solvent（TiF4）And lithium salts, stirring are added positive electrode and are sufficiently stirred, steam to after dissolving Precursors are obtained after hair solvent；The precursors are obtained after sintering to be coated with fluorine-containing titanium on positive electrode surface The positive active material of sour lithium layer；
（2）Solid-state electrolyte layer and negative plate containing solid electrolyte is set to be suppressed successively in containing the positive active material On positive plate, the solid lithium battery is obtained.
The disclosure also provides the solid lithium battery that above-mentioned method is prepared.
The inventor of the disclosure passes through numerous experiments, inadvertently finds, by using titanium tetrafluoride, lithium salts and anode After material mixes in the solution, by high temperature sintering, a layer thickness can be formed on the surface of positive electrode particle and uniformly contained Fluotitanic acid lithium layer.The positive electrode coated by fluorine-containing lithium titanate can avoid that boundary occurs between positive electrode and solid electrolyte Face side reaction prevents the elements diffusion between interface, substantially reduces the interface impedance between positive electrode and solid electrolyte.And this Open proposition uses titanium tetrafluoride（TiF4）, high temperature sintering prepares positive electrode after lithium salts mixes in the solution with positive electrode The method that surface is coated with the positive active material of fluorine-containing metatitanic acid lithium layer can uniformly wrap the surface of positive electrode It covers, obtains the controllable positive electrode of coating thickness, it can be to avoid positive material when by the positive electrode for solid lithium battery Interfacial reaction or elements diffusion occur between material and solid electrolyte, reduces interface impedance, improves the stable circulation of positive electrode Property, extend the service life of solid lithium battery, improves the chemical property of solid lithium battery.
Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the disclosure is described in detail below.It should be understood that described herein specific Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of solid lithium battery, including positive plate, negative plate and solid-state electrolyte layer, the positive plate Including positive active material, the positive active material includes positive electrode particle and is coated on the positive electrode particle surface Fluorine-containing metatitanic acid lithium layer.
The solid lithium battery of the disclosure coats the positive electrode of fluorine-containing metatitanic acid lithium layer, the coating thickness using surface Uniformly, it can prevent the elements diffusion between interface to avoid interfacial reaction occurs between positive electrode and solid electrolyte, drop significantly Interface impedance between low positive electrode and solid electrolyte improves the cyclical stability of positive electrode, extends all-solid-state battery Service life, and improve its chemical property.
According to the disclosure, the fluorine-containing metatitanic acid lithium layer be the positive electrode particle through titanium tetrafluoride and lithium salts processing after The lithium titanate clad for the doping fluorine that surface is formed；The F/O atomic ratios of the fluorine-containing metatitanic acid lithium layer refer to the anode that test obtains Fluorine element accounts for all atomic percentage contents in material surface divided by oxygen element accounts for the value that all elements percentage composition obtains, and F/O is former Fluorine content of the son than that can characterize fluorine-containing metatitanic acid lithium layer, the F/O atomic ratios can be by well-known to those skilled in the art Method measures to obtain, for example, the F/O atomic ratios described in the disclosure are to measure to obtain by X-ray photoelectron spectroscopic analysis method 's.Covered effect is uniform, it is preferable that the F/O atomic ratios of the fluorine-containing metatitanic acid lithium layer can be 0.01-100, and fluorine contains in clad Amount does not change with coating thickness.
According to the disclosure, in the fluorine-containing lithium titanate clad, the molar ratio of fluorine atom and titanium atom can be in very big model Enclose interior variation, preferably 0.01-2.4：1.
According to the disclosure, the grain size of the positive active material can change in very large range, preferably 0.05-1000 μm, further preferably 1-100 μm；The thickness of fluorine-containing metatitanic acid lithium layer is controllable, can also change in very large range, in order into one Equably clad anode material is walked, interfacial reaction is avoided, it is preferable that the thickness of the fluorine-containing metatitanic acid lithium layer is 10nm-2000nm, Further preferably 50-1000nm.
According to the disclosure, the lithium salts is specifically as follows Li2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、 Li2SO4、Li3PO4、LiNO3, lithium acetate, lithium methoxide, lithium ethoxide, at least one of lithium citrate and lithium amide.
According to the disclosure, solid-state electrolyte layer is Fast ion conductor structural type（NASICON types）Solid electrolyte, calcium titanium One or more of mine type solid electrolyte, sulphur system solid electrolyte.
The NASICON types solid electrolyte is LiM2(PO4)3And its at least one of dopant, wherein M Ti, At least one of Zr, Ge, Sn or Pb；The LiM2(PO4)3Dopant use doped chemical be selected from Mg, Ca, Sr, Ba, At least one of Sc, Al, Ga, In, Nb, Ta, V.
The spacious type solid electrolyte of calcium titanium is 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 higher than at least one of 0, A Li, Na elements, B For at least one of La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element, at least one in M Sr, Ca, Ba, Ir, Pt element Kind, at least one of D Nb, Ta elements.
The sulfur-bearing solid electrolyte that sulphur system solid electrolyte can be well known to those skilled in the art, is preferably tied The Li of brilliant titaniumxMyPzSw, glassy state Li2S-P2S5, glass ceramics state Li2S-P2S5At least one of, wherein M can be At least one of Si, Ge and Sn, x+4y+5z=2w, 2≤x≤11,0≤y≤1.5,0≤z≤3,3≤w≤13；
The Li of the crystallization titaniumxMyPzSwThe Li of crystalline state can be selected from3PS4, crystalline state Li4SnS4, crystalline state Li4GeS4、 The Li of crystalline state10SnP2S12, crystalline state Li10GeP2S12With the Li of crystalline state10SiP2S12At least one of；The glass The Li of state2S-P2S570Li selected from glassy state2S-30P2S5, glassy state 75Li2S-25P2S5With the 80Li of glassy state2S- 20P2S5At least one of；The Li of the glass ceramics state2S-P2S570Li selected from glass ceramics state2S-30P2S5, glass pottery The 75Li of porcelain state2S-25P2S5With the 80Li of glass ceramics state2S-20P2S5At least one of.
According to the disclosure, the positive electrode is not particularly limited, and can be the positive electrode of this field conventional kind, It is preferably selected from LiCoO2、LiNiO2、LiMn2O4、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、 Li5FeO4、TiS2、V2S3、FeS、FeS2、TiO2、Cr3O8、V2O5、MnO2、LiCoxNi1-xO2、LiCoxNi1-x-yAlyO2、 LiFepMnqX1-p-qO4、Li1+sL1-p-qMpNqO2And LiYSrAt least one of；
Wherein, 0≤x≤1,0≤y≤1,0≤p≤1,0≤q≤1,0≤p+q≤1, -0.1≤s≤0.2,1≤r≤2.5；
X be Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo at least one, L, M, N be each independently Li, Co, Mn, Ni, Fe, At least one of Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, at least one of Y Ti, Fe, Ni, Cu, Mo.
In order to further increase the stability of positive plate, it is preferable that the positive plate can also include positive conductive agent and The content of first binder, positive conductive agent and first binder can change in very large range, under preferable case, relative to The content of positive active material described in 100 parts by weight, the positive conductive agent can be 0.1-20 parts by weight, and described first bonds The content of agent can be 0.01-10 parts by weight.
The meaning of positive conductive agent and first binder is well known to those skilled in the art, and can be conventional kind, this Special requirement is not done in invention, and positive conductive agent is preferably at least one of acetylene black, carbon nanotube, carbon fiber and carbon black； First binder is preferably at least one of polyvinylidene fluoride, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber.
According to the disclosure, in order to improve the stability and electrical property of solid-state electrolyte layer, it is preferable that the solid electrolyte Layer can also include the second binder, and the dosage of the second binder can be the conventional amount used of this field, it is preferable that relative to The content of solid electrolyte described in 100 parts by weight, second binder can be 0.01-10 parts by weight.
Second binder can be the binder of this field conventional kind, be preferably selected from polythiophene, polypyrrole, gather Tetrafluoroethene, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, Styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin, acrylic acid tree Fat, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, carboxymethyl cellulose At least one of sodium and styrene-butadiene latex.
According to the disclosure, the negative plate includes negative current collector and the negative electrode material layer positioned at negative current collector surface, The negative electrode material layer is lithium or lithium alloy or the negative electrode material layer includes negative electrode active material and third binder；
In the another embodiment of the disclosure, negative electrode material layer can be include negative electrode active material, third binder Layer, wherein the relative amount of negative electrode active material and third binder can change in very large range, under preferable case, phase For negative electrode active material described in 100 parts by weight, the content of the third binder can be 0.01-10 parts by weight.
According to the disclosure, what negative electrode active material can be well known to those skilled in the art is used for the normal of lithium ion battery Type is advised, at least one of carbon material, tin alloy, silicon alloy, silicon, tin and germanium are preferably selected from, as people in the art The common knowledge of member also contains cathode conductive agent when negative electrode active material uses silicon class material in the negative electrode material layer, Effect and specific type are known to those skilled in the art, and details are not described herein again.
The various negative electrode binders that the third binder can be known to the skilled person, preferably polythiophene, Polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene Copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin, Acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, sodium carboxymethylcellulose At least one of with styrene-butadiene latex.
The disclosure also provides a kind of method preparing solid lithium battery, and the solid lithium battery includes positive plate, bears Pole piece and solid-state electrolyte layer, this method comprises the following steps：
（1）Titanium tetrafluoride and lithium salts are added into solvent, stirring is added positive electrode and is sufficiently stirred, evaporate solvent to after dissolving After obtain precursors；The precursors are obtained after sintering to be coated with fluorine-containing metatitanic acid lithium layer on positive electrode surface （F- Li4Ti5O12Layer）Positive active material；
（2）Solid-state electrolyte layer and negative plate containing solid electrolyte is set to be suppressed successively in containing the positive active material On positive plate, the solid lithium battery is obtained.
The preparation method of the disclosure obtains to surface to be coated with and contains using can uniformly be modified the surface of positive electrode The controllable positive active material of fluotitanic acid lithium layer thickness, can be to avoid just when by the positive active material for solid lithium battery With solid electrolyte interfacial reaction or elements diffusion occur for pole material, reduce interface impedance.
In addition to the preparation method of the disclosure, chemical vapour deposition technique, chemical gaseous phase conveying or vacuum laser can also be used The methods of sputtering prepares the positive active material that surface coats fluorine-containing metatitanic acid lithium layer, but the cost of the above method is very high. And when using preparation method described in the disclosure, it can be evenly coated and fluorine-containing metatitanic acid lithium layer that thickness is controllable, while institute The raw material used is simple, and has significant cost advantage.
According to the disclosure, the lithium salts can be Li2O、Li2S、LiOH、LiF、LiCl、LiBr、LiI、Li2CO3、 Li2SO4、Li3PO4、LiNO3, lithium acetate, lithium methoxide, lithium ethoxide, at least one of lithium citrate and lithium amide.
According to the disclosure, the solvent is at least one of water, methanol, ethyl alcohol, lithium citrate and lithium amide.
According to the disclosure, in order to further enhance the interface performance between positive electrode and solid electrolyte, the electrolysis Matter layer is at least one of NASICON types solid electrolyte, Ca-Ti ore type solid electrolyte, sulphur system solid electrolyte.
Wherein, the NASICON types solid electrolyte is LiM2(PO4)3And its at least one of dopant, wherein M are Ti, Zr, Ge, Sn or Pb, the doped chemical that the dopant uses is in Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V At least one.
The chemical formula of the spacious type solid electrolyte of calcium titanium is 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 higher than 0；A is Li, Na member At least one of element, at least one of B La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element, M Sr, Ca, Ba, Ir, Pt At least one of element, at least one of D Nb, Ta elements.
The sulfur-bearing solid electrolyte that sulphur system solid electrolyte can be well known to those skilled in the art, is preferably tied The Li of crystalline statexMyPzSw, glassy state Li2S-P2S5, glass ceramics state Li2S-P2S5At least one of, wherein M is Si, Ge At least one of with Sn, x+4y+5z=2w, 2≤x≤11,0≤y≤1.5,0≤z≤3,3≤w≤13；Wherein, the crystallization The Li of statexMyPzSwLi selected from crystalline state3PS4, crystalline state Li4SnS4, crystalline state Li4GeS4, crystalline state Li10SnP2S12, crystalline state Li10GeP2S12, crystalline state Li10SiP2S12At least one of；The Li of the glassy state2S- P2S570Li selected from glassy state2S-30P2S5, glassy state 75Li2S-25P2S5, glassy state 80Li2S-20P2S5In at least It is a kind of；The Li of the glass ceramics state2S-P2S570Li selected from glass ceramics state2S-30P2S5, glass ceramics state 75Li2S- 25P2S5, glass ceramics state 80Li2S-20P2S5At least one of.
The positive electrode is not particularly limited, and can be the positive electrode of this field conventional kind, preferably described Positive electrode is selected from LiCoO2、LiNiO2、LiMn2O4、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、 Li2CuO2、Li5FeO4、TiS2、V2S3、FeS、FeS2、TiO2、Cr3O8、V2O5、MnO2、LiCoxNi1-xO2、LiCoxNi1-x- yAlyO2、LiFepMnqX1-p-qO4、Li1+sL1-p-qMpNqO2And LiYSrAt least one of；Wherein, 0≤x≤1,0≤y≤1,0 ≤ p≤1,0≤q≤1,0≤p+q≤1, -0.1≤s≤0.2,1≤r≤2.5, X Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or At least one of Mo, L, M, N are each independently Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B At least one of, at least one of Y Ti, Fe, Ni, Cu, Mo.
According to the disclosure, step（1）In, the reaction condition of the positive electrode and titanium tetrafluoride can be in very large range Variation, as long as meeting can make the titanium tetrafluoride on positive electrode surface and lithium salts react.Preferred reaction condition packet It includes：Solvent evaporating temperature is 20-100 DEG C, and sintering temperature is 400-1000 DEG C；More preferably include：Evaporating temperature is 70-90 DEG C, Sintering temperature is 650-850 DEG C.
The inventor of the disclosure has found in an experiment, when positive electrode and lithium salts, the catalytic condition control of titanium tetrafluoride In above range, the positive electrode after being handled by fluorine-containing lithium titanate has system between positive electrode and solid electrolyte More excellent interfacial effect.
The positive electrode can change in very large range with the relative usage of the lithium salts and titanium tetrafluoride, in order into One step improves reaction efficiency, it is preferable that positive electrode, titanium tetrafluoride and lithium salts（In terms of elemental lithium）Dosage molar ratio can be 1：（0.01-100）：（0.01-100）.
According to the disclosure, the preparation method of positive plate can also include：Make the positive active material, positive conductive agent and First binder is coated on the surface of plus plate current-collecting body after mixing in a solvent, is contained after dry and compressing tablet process The positive plate of positive electrode active material layer；
The relative usage of above-mentioned positive active material, positive conductive agent and first binder can change in very large range, excellent Selection of land, relative to positive active material described in 100 parts by weight, the dosage of the positive conductive agent can be 0.1-20 parts by weight, The dosage of the first binder can be 0.01-10 parts by weight；In above-mentioned preferred amount ranges, it is prepared by the above method The positive chip architecture arrived is more stable and electrical property is more preferable.
Wherein, positive conductive agent and first binder can be this field conventional kind, it is preferable that the positive conductive agent Can be at least one of acetylene black, carbon nanotube, carbon fiber and carbon black；The first binder can be to gather inclined difluoro second At least one of alkene, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber.
According to the disclosure, the preparation method of solid-state electrolyte layer can also include：The solid electrolyte and second is set to glue The surface that agent is coated on the positive plate after mixing in a solvent is tied, is obtained after dry and compressing tablet process containing solid-state electricity Solve the positive plate of matter layer；
The relative usage of above-mentioned solid electrolyte and the second binder can change in very large range, it is preferable that relative to 100 The dosage of solid electrolyte described in parts by weight, second binder can be 0.01-10 parts by weight；Above-mentioned preferred dosage model In enclosing, the solid-state electrolyte layer charge-discharge performance being prepared by the above method is more preferable.
Wherein, the second binder can be this field conventional kind, it is preferable that second binder can be selected from poly- Thiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-the third Alkene-diene copolymer resins, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, gathers styrene butadiene ribber Ester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyoxyethylene At least one of alkene, sodium carboxymethylcellulose and styrene-butadiene latex.
According to the disclosure, including negative current collector and the negative electrode material layer positioned at negative current collector surface, the cathode material The bed of material is lithium or lithium alloy or the negative electrode material layer includes negative electrode active material and third binder；
When the negative electrode material layer includes negative electrode active material and third binder, the preparation method of negative plate can also include： The negative electrode active material and third binder is set to be coated on the surface of negative current collector after mixing in a solvent, through drying With the negative plate is obtained after compressing tablet process.
The relative usage of above-mentioned negative electrode active material and third binder can change in very large range, it is preferable that phase For negative electrode active material described in 100 parts by weight, the dosage of the third binder is 0.01-10 parts by weight.
Wherein, negative electrode active material and third binder can be this field conventional kind, it is preferable that the negative electrode active Substance can be selected from least one of carbon material, tin alloy, silicon alloy, silicon, tin and germanium；The third binder can be Polythiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-the third Alkene-diene copolymer resins, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, gathers styrene butadiene ribber Ester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, carboxymethyl are fine Dimension plain at least one of sodium and styrene-butadiene latex.As the common knowledge of those skilled in the art, when negative electrode active material uses When silicon class material, cathode conductive agent is also contained in the negative electrode material layer, effect and specific type and content are this field skill Well known to art personnel, details are not described herein again.
The disclosure also provides the solid lithium battery that above-mentioned method is prepared.
The disclosure is further described by the following examples, but the disclosure is not therefore any way limited.
Embodiment 1
（1）Contain F- Li4Ti5O12The preparation of the positive active material of layer
By 100 g（Gram）Positive electrode active materials LiCoO2, 12 g TiF4It uniformly mixes, and is added with the anhydrous LiOH of 2 g To being stirred in the ethyl alcohol of 500 mL, mixing time is 2 h, is evaporated under 70 degrees Celsius, gained predecessor is fully ground High temperature sintering is carried out after mill under 700 degrees Celsius, gained final product is F-Li4Ti5O12The LiCoO that material is coated2Anode Material.
（2）The preparation of positive plate C
930g is contained by F-Li4Ti5O12The LiCoO that material is coated2Positive electrode（93%）, 30 g bonding agents PVDF （3%）, 20 g acetylene blacks（2%）, 20 g conductive agent carbon fibers（2%）It is added to 1500 g solvents NMP（N-methyl pyrrolidones） In, it is then stirred in de-airing mixer, forms the anode sizing agent of stable uniform.The anode sizing agent is equably intermittently coated on Aluminium foil（Aluminium foil size is：160 mm of width, 16 μm of thickness）Two sides on, then 393 K dry, after roll squeezer tabletting Obtain C.
（3）The preparation of positive plate CE containing solid-state electrolyte layer
In glove box, by the 70Li of the glassy state of 600 g2S-30P2S5In the toluene solution of 1200 g, wherein toluene solution In contain 30 g butadiene rubber binders, then heating stirring to stabilization, uniform solution.The solution is continuously coated on step On rapid 2 obtained positive plate C, then 333 K are dried, and it is 485 mm to cut out as size（It is long）×46 mm（It is wide）Contain solid-state The positive plate CE of electrolyte layer.
（4）The preparation of cathode A
By 940 g negative electrode active material artificial graphites（94%）, 30 g bonding agents CMC（3%）With 30 g bonding agents SBR（3%）It is added It into 1200 g deionized waters, is then stirred in de-airing mixer, forms the negative electrode slurry of stable uniform.The slurry is uniform Ground interval is coated on copper foil（Copper foil size is：160 mm of width, 16 μm of thickness）Two sides on, then 393 K dry, pass through After roll squeezer tabletting, it is 480 mm to cut out as size（It is long）×45 mm（It is wide）Negative plate A.
（5）The preparation of solid lithium battery CEA
It in glove box, is aligned and is placed in hot press after the CE that step 3 obtains and the A that step 4 obtains are cut out, carry out 423 1 h of K hot pressing, is honored as a queen using aluminum plastic film vacuum-pumping density, takes out sample.By above-mentioned pressed sample 200 in isostatic pressing machine After MPa, compacting in 300 seconds, the solid lithium battery CEA1 of the present embodiment is obtained.
Embodiment 2
The electrolyte and lithium ion battery of the present embodiment are prepared using the method in embodiment 1, the difference is that：Step（1） In, by TiF4It is changed to 6 g and 1 g respectively with the dosage of anhydrous LiOH, other steps and operation all same.Obtain the present embodiment Solid lithium battery CEA2.
Embodiment 3
The electrolyte and lithium ion battery of the present embodiment are prepared using the method for embodiment 1, the difference is that：Step（1）In, Positive electrode uses LiFePO4Replace LiCoO2.Obtain the solid lithium battery CEA3 of the present embodiment.
Embodiment 4
The electrolyte and lithium ion battery of the present embodiment are prepared using the method for embodiment 1, the difference is that：Step（1）In, Gained predecessor is subjected to high temperature sintering in the case of 900 degrees Celsius, other steps and operation all same.Obtain the present embodiment Solid lithium battery CEA4.
Comparative example 1
The electrolyte and lithium ion battery of the present embodiment are prepared using the method for embodiment 1, the difference is that：Step（1）In, 12gTiF is substituted using four fourth fat of 285ml metatitanic acids4。
Comparative example 2
The electrolyte and lithium ion battery of the present embodiment are prepared using the method for embodiment 1, the difference is that：Step（1）In, Use LiCoO2Material directly carries out the anode making of C, the making of CE, the making of cathode A and the making of CEA, not right LiCoO2Carry out F-Li4Ti5O12Cladding operation.
Testing example 1
Anode to embodiment 1-4 the obtained positive active materials containing fluorination decorative layer and being obtained in comparative example 1-2 respectively Active material carries out SEM tests and XPS tests, obtains the atomic ratio, grain size and fluorination modification of the surface F/O of positive active material Thickness degrees of data is listed in table 1；
Above-mentioned positive active material is subjected to Ar+After ion(ic) etching, the atomic ratio of its surface F/O, wherein Ar are tested+Ion(ic) etching Step-length be 2 min, used ion beam energy be 2 keV.
Table 1
。
Testing example 2
The cycle life of battery is carried out to the solid lithium battery CEA1-CEA5 obtained in embodiment 1-3 and comparative example 1-2 Test, test method are as follows：
The battery that each embodiment and comparative example is prepared respectively is taken 20, in LAND CT 2001C secondary cell performance detections On device, under the conditions of 298 ± 1 K, battery is subjected to charge and discharge cycles test with 0.1 C.Steps are as follows：Shelve 10 min； Constant-voltage charge is to 4.2 V/0.05 C cut-offs；Shelve 10 min；Constant-current discharge is to 3.0 V, as 1 time cycle.The step is repeated, In cyclic process when battery capacity 80% less than discharge capacity for the first time, loop termination, the cycle-index is the cycle of battery In the service life, every group is averaged.
Table 2
。
According to table 1- tables 2, the data comparison of embodiment 1-4 and comparative example 1-2 is understood：The all solid lithium electricity that the disclosure provides Pond has excellent cycle performance, and positive electrode is foring the fluorine-containing metatitanic acid lithium layer containing uniform fold just by surface treatment Pole active material.
The preferred embodiment of the disclosure described in detail above, still, the disclosure is not limited in the above embodiment Detail can carry out a variety of simple variants to the technical solution of the disclosure in the range of the technology design of the disclosure, this A little simple variants belong to the protection domain of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the disclosure to it is various can The combination of energy no longer separately illustrates.
In addition, arbitrary combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally Disclosed thought equally should be considered as disclosure disclosure of that.

Claims (18)

1. a kind of solid lithium battery, including positive plate, negative plate and solid-state electrolyte layer, which is characterized in that the positive plate Including positive active material, the positive active material includes positive electrode particle and is coated on the positive electrode particle surface Fluorine-containing metatitanic acid lithium layer.
2. solid lithium battery according to claim 1, which is characterized in that the fluorine-containing metatitanic acid lithium layer is the positive material Expect the clad of the lithium titanate for the doping fluorine that particle is formed after titanium tetrafluoride and lithium salts processing on surface.
3. solid lithium battery according to claim 1, which is characterized in that the fluorine atom and titanium atom in lithium titanate Molar ratio be 0.01-2.4：1.
4. solid lithium battery according to claim 1, which is characterized in that the grain size of the positive active material is 0.05-1000μm；The thickness of the fluorine-containing metatitanic acid lithium layer is 10-2000nm.
5. solid lithium battery according to claim 2, which is characterized in that the lithium salts is Li2O、Li2S、LiOH、LiF、 LiCl、LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3, lithium acetate, lithium methoxide, lithium ethoxide, lithium citrate and lithium amide At least one of.
6. solid lithium battery according to claim 1, which is characterized in that the F/O atomic ratios of the fluorine-containing metatitanic acid lithium layer For 0.01-100.
7. solid lithium battery according to claim 1, which is characterized in that the solid-state electrolyte layer is that the fast ion of sodium is led At least one of body structural type solid electrolyte, Ca-Ti ore type solid electrolyte, sulphur system solid electrolyte.
8. solid lithium battery according to claim 7, which is characterized in that the Fast ion conductor structural type solid-state electricity Solution matter is LiM2(PO4)3And its at least one of dopant, wherein at least one of M Ti, Zr, Ge, Sn or Pb；Institute State LiM2(PO4)3Dopant use doped chemical in Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V at least It is a kind of；
The spacious type solid electrolyte of calcium titanium is 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 higher than at least one of 0, A Li, Na elements, B La, At least one of Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element, at least one of M Sr, Ca, Ba, Ir, Pt element, D is At least one of Nb, Ta element；
Sulphur system solid electrolyte is the Li of crystalline statexMyPzSw, glassy state Li2S-P2S5, glass ceramics state Li2S-P2S5 At least one of, wherein M is at least one of Si, Ge and Sn, x+4y+5z=2w, 2≤x≤11,0≤y≤1.5,0≤z ≤ 3,3≤w≤13；
The Li of the crystalline statexMyPzSwLi selected from crystalline state3PS4, crystalline state Li4SnS4, crystalline state Li4GeS4, crystallization The Li of state10SnP2S12, crystalline state Li10GeP2S12With the Li of crystalline state10SiP2S12At least one of；The glassy state Li2S-P2S570Li selected from glassy state2S-30P2S5, glassy state 75Li2S-25P2S5With the 80Li of glassy state2S-20P2S5In At least one；The Li of the glass ceramics state2S-P2S570Li selected from glass ceramics state2S-30P2S5, glass ceramics state 75Li2S-25P2S5With the 80Li of glass ceramics state2S-20P2S5At least one of.
9. solid lithium battery according to claim 1, which is characterized in that the positive electrode is selected from LiCoO2、 LiNiO2、LiMn2O4、LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4、TiS2、V2S3、 FeS、FeS2、TiO2、Cr3O8、V2O5、MnO2、LiCoxNi1-xO2、LiCoxNi1-x-yAlyO2、LiFepMnqX1-p-qO4、Li1+ sL1-p-qMpNqO2And LiYSrAt least one of；
Wherein, 0≤x≤1,0≤y≤1,0≤p≤1,0≤q≤1,0≤p+q≤1, -0.1≤s≤0.2,1≤r≤2.5；
X be Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo at least one, L, M, N be each independently Li, Co, Mn, Ni, Fe, At least one of Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, at least one of Y Ti, Fe, Ni, Cu, Mo.
10. solid lithium battery according to claim 1, which is characterized in that the positive plate further includes positive conductive agent And first binder, relative to positive active material described in 100 parts by weight, the content of the positive conductive agent is 0.1-20 weight Part, the content of the first binder is 0.01-10 parts by weight；
The positive conductive agent is at least one of acetylene black, carbon nanotube, carbon fiber and carbon black；The first binder is At least one of polyvinylidene fluoride, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber.
11. solid lithium battery according to claim 1, which is characterized in that the solid-state electrolyte layer further includes second Binder, relative to solid electrolyte described in 100 parts by weight, the content of second binder is 0.01-10 parts by weight；
Second binder is selected from polythiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, gathers 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 At least one of cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethylcellulose and styrene-butadiene latex.
12. solid lithium battery according to claim 1, which is characterized in that the negative plate include negative current collector and Negative electrode material layer positioned at negative current collector surface, the negative electrode material layer are lithium or lithium alloy or the negative electrode material layer packet Include negative electrode active material and third binder.
13. solid lithium battery according to claim 1, which is characterized in that it is characterized in that, relative to 100 parts by weight The content of the negative electrode active material, the third binder is 0.01-10 parts by weight；
The negative electrode active material is selected from least one of carbon material, tin alloy, silicon alloy, silicon, tin and germanium；The third Binder is selected from polythiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polystyrene, polypropylene Amide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, poly- second Alkene pyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl are fine At least one of dimension element, sodium carboxymethylcellulose and styrene-butadiene latex.
14. a kind of method preparing solid lithium battery, the solid lithium battery includes positive plate, negative plate and solid state electrolysis Matter layer, which is characterized in that this method comprises the following steps：
（1）Titanium tetrafluoride and lithium salts are added into solvent, stirring is added positive electrode and is sufficiently stirred, evaporate solvent to after dissolving After obtain precursors；The precursors are obtained after sintering to be coated with fluorine-containing metatitanic acid lithium layer on positive electrode surface Positive active material；
（2）Solid-state electrolyte layer and negative plate containing solid electrolyte is set to be suppressed successively in containing the positive active material On positive plate, the solid lithium battery is obtained.
15. according to the method for claim 14, which is characterized in that the lithium salts is Li2O、Li2S、LiOH、LiF、LiCl、 LiBr、LiI、Li2CO3、Li2SO4、Li3PO4、LiNO3, lithium acetate, lithium methoxide, lithium ethoxide, in lithium citrate and lithium amide extremely Few one kind.
16. according to the method for claim 14, which is characterized in that step（1）In, the positive electrode and titanium tetrafluoride and The reaction condition that lithium salts is reacted includes：Evaporating temperature is 20-100 DEG C, and sintering temperature is 400-1000 DEG C, the anode material Material, titanium tetrafluoride and lithium salts dosage（Based on elemental lithium）Molar ratio be 1：（0.01-100）：（0.01-100）.
17. according to the method for claim 14, which is characterized in that the solid-state electrolyte layer is Fast ion conductor structure At least one of type solid electrolyte, Ca-Ti ore type solid electrolyte, sulphur system solid electrolyte.
18. the solid lithium battery that the method described in any one of claim 14-17 is prepared.
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