CN109004174A - Positive plate, preparation method thereof and all-solid-state lithium secondary battery using positive plate - Google Patents

Positive plate, preparation method thereof and all-solid-state lithium secondary battery using positive plate Download PDF

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Publication number
CN109004174A
CN109004174A CN201710431635.0A CN201710431635A CN109004174A CN 109004174 A CN109004174 A CN 109004174A CN 201710431635 A CN201710431635 A CN 201710431635A CN 109004174 A CN109004174 A CN 109004174A
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positive plate
lithium metal
positive
anode layer
lithium
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刘成勇
郭永胜
王喜庆
蔡挺威
梁成都
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
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Abstract

A positive electrode sheet, a method for producing the same, and an all-solid-state lithium secondary battery using the positive electrode sheet. The invention discloses a positive plate which can be applied to an all-solid-state lithium secondary battery and comprises a positive current collector and a composite positive plate layer distributed on the positive current collector, wherein the composite positive plate layer consists of a high-potential positive plate layer with the working potential of more than 3.8V distributed on the positive current collector and a low-potential positive plate layer with the working potential of less than or equal to 3.8V distributed on the high-potential positive plate layer. Compared with the prior art, the positive plate adopts the low-potential positive layer to coat the high-potential positive layer, separates the high-potential positive material from the polymer solid electrolyte, avoids the electrochemical oxidative decomposition of the polymer solid electrolyte, and improves the cycle life of the all-solid-state lithium secondary battery and the energy density of the battery. In addition, the invention also discloses a preparation method of the positive plate and an all-solid-state lithium secondary battery using the positive plate.

Description

Positive plate and preparation method thereof and all solid lithium secondary battery for using positive plate
Technical field
The invention belongs to field of batteries, it is more particularly related to a kind of positive plate and preparation method thereof and make With all solid lithium secondary battery of the positive plate.
Background technique
Lithium secondary battery because have output power, energy density height, long service life, average output voltage it is high, oneself Discharge small, memory-less effect, can be quickly charged and discharged, the advantages that cycle performance is superior and non-environmental-pollution, have become digital electricity The first choice of sub- product rechargable power supplies, is also considered as most competitive Vehicular dynamic battery.
Currently, lithium secondary battery mainly uses liquid electrolyte material, contains a large amount of organic solvents in liquid electrolyte, lead It is prominent to send a telegraph pond security risk.Due to the safety that all solid lithium secondary battery has liquid lithium secondary battery incomparable, and It is expected to thoroughly eliminate the security risk in use process, more meets the demand of electric car and scale energy storage field future development.
Solid electrolyte is many kinds of, wherein polyethylene oxide (PEO) quasi polymer electrolyte has the advantage that PEO Polymer flexibility with higher when system is as skeleton, polymer electrolyte system lithium ion conductivity with higher, There is preferable interface compatibility with the electrode of the low-work voltages such as lithium metal, graphite.But the oxidative resistance of PEO system is stablized Property is poor, will appear the electrochemical decomposition of PEO in 3.8V or so.Therefore, the polymeric system based on PEO skeleton is only capable of using at present In LiFePO4 (LiFePO4) etc. low-voltages positive electrode system, can not be applied in high voltage system, cause polymer solid The energy density of state battery is difficult to improve.
Currently, the prior art uses the polymer electrolyte of high-voltage-stable type, such as polycarbonate, Kynoar As the electrolyte of solid state battery, still, that there are glass transition temperatures is high for these materials, easily crystallization, lithium ion conductivity are low etc. is asked Topic.In order to improve conductivity, needs to be added liquid electrolyte for polymer and be prepared into gel electrolyte, but introduce liquid electrolyte After matter, the safety of solid polymer cell, and and unresolved polymer dielectric answering in high-tension battery system will be weakened With.
In view of this, it is necessory to provide a kind of positive plate with good chemical property and preparation method thereof and make With all solid lithium secondary battery of the positive plate.
Summary of the invention
It is an object of the invention to: it overcomes the deficiencies of existing technologies, a kind of anode with good chemical property is provided Piece and preparation method thereof and all solid lithium secondary battery for using the positive plate.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of positive plate, it can be applied to all solid lithium secondary battery, It includes plus plate current-collecting body and the anode composite layer that is distributed on plus plate current-collecting body, and anode composite layer is by being distributed in plus plate current-collecting body On high potential anode layer of the operating potential greater than 3.8V and the operating potential that is distributed in high potential anode layer be less than or equal to The low potential anode layer of 3.8V forms.
Positive plate of the present invention select low potential, low oxidative anode layer as low potential anode layer, with polymer solid Electrolyte layer directly contacts, and selects the anode layer of high potential, high oxidative as high potential anode layer, as battery energy density The carrier of promotion.Anode layer current potential height judgment criteria is: with the operating potential of lithium metal for 0V, the operating potential of anode layer is Difference of the positive electrode active materials relative to the operating potential of lithium metal, the higher anode layer of difference is high potential layer anode layer, poor Being worth lower anode layer is low potential anode layer.Low potential anode layer is directly contacted with solid polyelectrolyte layer, low potential The operating potential of anode layer is less than or equal to 3.8V, therefore weak to the oxidisability of solid polyelectrolyte layer, if low potential is just The operating voltage of pole layer is greater than 3.8V, and the polyelectrolyte floor contacted with low potential anode layer is easy to cause to decompose, into One step leads to the too fast decaying of battery.
As a kind of improvement of positive plate of the present invention, the thickness of the high potential anode layer and low potential anode layer is respectively 10~200 μm.Anode layer is excessively thin, will lead to battery energy density reduction；Anode layer is blocked up, will lead to lithium ion in anode layer and passes Defeated impedance increases, and battery polarization is serious.
As a kind of improvement of positive plate of the present invention, the high potential anode layer contains high potential positive electrode, inorganic solid Body electrolyte, conductive agent and binder, high potential positive electrode, inorganic solid electrolyte, conductive agent, binder mass ratio be 48~90:8~50:1~10:1~10, preferably 60~75:15~30:5:5.
As a kind of improvement of positive plate of the present invention, the high potential positive electrode is selected from layered lithium metal oxides, point Spinel structure lithium metal oxide, lithium metal phosphates, lithium metal are fluorinated sulfate, lithium metal vanadate and to Layered Lithium gold Belong to oxide, spinel structure lithium metal oxide, lithium metal phosphates, lithium metal fluorination sulfate, lithium metal vanadate At least one of modified material.
As a kind of improvement of positive plate of the present invention, layered lithium metal oxide is selected from cobalt acid lithium LiCoO2, nickel acid Lithium LiNiO2, ternary material LiNimBnC(1-m-n)O2At least one of, wherein B, C are respectively selected from least one in Co, Al, Mn Kind, and B and C be not identical, 0 < m < 1,0 < n < 1；The spinel structure lithium metal compounds are selected from LiMn2O4 LiMn2O4And/or nickel LiMn2O4 LiNi0.5Mn1.5O4；The lithium metal phosphates are selected from cobalt phosphate lithium LiCoPO4And/or LiNiPO LiNiPO4；Institute It states lithium metal fluorination sulfate and is selected from fluorination cobaltous sulfate lithium LiCoFSO4；The lithium metal vanadate is selected from vanadic acid nickel lithium LiNiVO4；The modified material is selected to layered lithium metal oxides, spinel structure lithium metal oxide, lithium metal phosphoric acid The element of salt, lithium metal fluorination sulfate or lithium metal vanadic acid salt dopping and cladding treated material, doping and cladding is selected from At least one of Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W.
As a kind of improvement of positive plate of the present invention, the low potential anode layer contains low potential positive electrode, inorganic solid Body electrolyte, conductive agent and binder, low potential positive electrode, inorganic solid electrolyte, conductive agent and binder mass ratio For 48~90:8~50:1~10:1~10, preferably 60~75:15~30:5:5.
As a kind of improvement of positive plate of the present invention, the low potential positive electrode is selected from LiFePO4 (LiFePO4), phosphorus Sour iron (FePO4), lithium titanate (Li4Ti5O12), vanadic anhydride (V2O5), metal sulfide, at least one in thiophosphate Kind.
As a kind of improvement of positive plate of the present invention, the metal sulfide is selected from CuS2、FeS2、MoS2、NiS、TiS2In At least one；The thiophosphate is selected from Li2FeP2S6And/or LiTi2(PS4)3。
As a kind of improvement of positive plate of the present invention, the inorganic solid electrolyte is selected from the fast lithium ion conductor of oxide And/or the fast lithium ion conductor of sulfide, wherein the fast lithium ion conductor of oxide is selected from NASICON (Na+super ionic Conductor) structure, LISICON (Li+Super ionic conductor) structure, garnet (Garnet) structure, calcium titanium At least one of mine (Pervoskite) structure；The fast lithium ion conductor of sulfide is selected from yLi2S-(100-y)P2S5With MS2Or The mixed system of LiqQ, wherein 1 < y < 100, M are selected from Si, Ge or Sn, and Q is selected from F, Cl, Br, I, O, N, PO4 3-、SO4 2-、BO3 3- Or SiO4 4-, q be 1~4 natural number.
As a kind of improvement of positive plate of the present invention, the fast lithium ion conductor of oxide is selected from LiM2(PO4)3D、Li14Zn (GeO4)4、Li7La3A2O12、Li3xLa1-3xTiO3At least one of, wherein D is selected from Ti, Zr or Ge, and A is selected from transition metal, Such as Zr, Sn, 0 < x < 0.16.
As a kind of improvement of positive plate of the present invention, the conductive agent is selected from super-P, acetylene black, VGCF or carbon nanometer Pipe；The binder is selected from PVDF, PAALi, PVDF-HFP, butadiene-styrene rubber, nitrile rubber or polyurethane.
In order to achieve the above-mentioned object of the invention, the present invention also provides a kind of preparation methods of aforementioned positive electrode piece comprising with Lower step:
1) positive electrode of high potential anode layer, inorganic solid electrolyte, conductive agent, binder is mixed with certain mass ratio After conjunction, suitable organic solvent is added and is mixed and made into slurry, be coated on plus plate current-collecting body surface, be compacted after dry, high electricity is made Position anode layer；And
2) positive electrode of low potential anode layer, inorganic solid electrolyte, conductive agent, binder is mixed with certain mass ratio After conjunction, suitable organic solvent is added and is mixed and made into slurry, high potential anode layer surface is coated on certain thickness ratio and is formed Low potential anode layer is compacted obtain the positive plate containing anode composite layer after dry in protective gas.
Positive electrode, nothing in a kind of improvement of preparation method as positive plate of the present invention, the step 1) and step 2) Machine solid electrolyte, conductive agent, binder mass ratio be 48~90:8~50:1~10:1~10, preferably 60~75:15~ 30:5:5。
A kind of improvement of preparation method as positive plate of the present invention, the dosage of the organic solvent is according to the viscosity of slurry Regulated and controled, the viscosity for controlling slurry is 5000~200000mPas, preferably 10000~50000mPas.Slurry viscosity mistake Greatly, pole piece manufacture difficulty is increased, viscosity is too low, is easy to cause positive electrode content on unit area to reduce, reduces battery Energy density.
A kind of improvement of preparation method as positive plate of the present invention, the organic solvent are selected from ether organic solvent, hydrocarbon Class organic solvent, based organic solvent, nitrile organic solvent, amide-type organic solvent, alcohol organic solvent, halogenated organic solvent At least one of.
A kind of improvement of preparation method as positive plate of the present invention, the ether organic solvent are selected from ether, tetrahydro furan It mutters, at least one of glycol dimethyl ether；The hydrocarbon organic solvent is selected from pentane, n-hexane, hexamethylene, toluene, two At least one of toluene, trimethylbenzene；The based organic solvent is selected from ethyl acetate, methyl formate, butyl butyrate, adjacent benzene two At least one of formic acid dimethyl ester；The nitrile organic solvent is selected from acetonitrile；The amide-type organic solvent is selected from N- methyl Pyrrolidones (NMP) and/or N,N-dimethylformamide (DMF)；The alcohol organic solvent is selected from ethyl alcohol；It is described halogenated organic Solvent is selected from methylene chloride and/or 1,2- dichloroethanes.
A kind of improvement of preparation method as positive plate of the present invention, the protective gas be nitrogen or inert gas, it is lazy The property preferred argon gas of gas；Compaction pressure is 20~500MPa, and preferably 200~300MPa, compacted density is 1.8~4.2g/cm3, Compacting temperature is 25~150 DEG C.
A kind of improvement of preparation method as positive plate of the present invention, the slurry hybrid mode can be using public in industry The mixing method known, such as magnetic agitation, mechanical ball mill.
In order to achieve the above-mentioned object of the invention, the present invention also provides a kind of all solid lithium secondary batteries comprising positive plate, Negative electrode tab and the solid polyelectrolyte layer being interval between positive plate and negative electrode tab, wherein positive plate is aforementioned positive electrode piece.
As a kind of improvement of all solid lithium secondary battery of the present invention, the solid polyelectrolyte layer includes polymer The mass ratio of ontology and lithium salts, polymer body and lithium salts is 20~80:80~20；Wherein, polymer body is selected from polyethers At least one of polymer, polyolefin polymers, polynitriles quasi polymer, polycarboxylate quasi polymer；Lithium salts is selected from LiPF6、LiBF4、LiClO4、LiAlCl4、LiSbF6、LiSCN、LiCF3SO3、LiCF3CO2、LiN(CF3SO2)2、LiAsF6、 LiBC4O8、LiN(FSO2)2, the fast lithium ion conductor of oxide, at least one of the fast lithium ion conductor of sulfide.
As a kind of improvement of all solid lithium secondary battery of the present invention, the fast lithium ion conductor of oxide is selected from NASICON(Na+Super ionic conductor) structure, LISICON (Li+Super ionic conductor) structure, stone At least one of garnet (Garnet) structure, perovskite (Pervoskite) structure；The fast lithium ion conductor of sulfide is selected from yLi2S-(100-y)P2S5With MS2Or the mixed system of LiqQ, wherein 1 < y < 100, M be selected from Si, Ge, Sn, Q be selected from F, Cl, Br、I、O、N、PO4 3-、SO4 2-、BO3 3-、SiO4 4-, q be 1~4 natural number.
As a kind of improvement of all solid lithium secondary battery of the present invention, the fast lithium ion conductor of oxide is selected from LiM2 (PO4)3D、Li14Zn(GeO4)4、Li7La3A2O12、Li3xLa1-3xTiO3At least one of, wherein D is selected from Ti, Zr or Ge, A Selected from transition metal, such as Zr, Sn, 0 < x < 0.16.
As a kind of improvement of all solid lithium secondary battery of the present invention, the polyether-based polymers are selected from polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyethylene glycol dimethyl ether (PEGDME), at least one in polysiloxanes Kind；The polyolefin polymers are selected from polyethylene (PE), polypropylene (PP), gather inclined tetrafluoroethene (PVDF), Kynoar- At least one of hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE) (PTFE), polyvinyl chloride (PVC)；The polynitriles Quasi polymer is selected from polyacrylonitrile (PAN) and/or poly- Melamine；The polycarboxylate quasi polymer is selected from polymethylacrylic acid Methyl esters (PMMA) and/or polymethyl acrylate (PMA)；The polycarbonate polymer be selected from polypropylene carbonate (PC) and/ Or poly- ethylenecarbonate (PEC).
As a kind of improvement of all solid lithium secondary battery of the present invention, the number-average molecular weight of the polymer is 40000~ 1000000, preferably 100000~600000.
As a kind of improvement of all solid lithium secondary battery of the present invention, the solid polyelectrolyte layer with a thickness of 5 ~500 μm, preferably 50~200 μm, the blocked up energy force density that will be greatly reduced finished battery of electrolyte layer, electrolyte layer are excessively thin It then will increase the risk of battery internal short-circuit.
As a kind of improvement of all solid lithium secondary battery of the present invention, the negative electrode tab includes negative current collector and is coated on Negative electrode layer on negative current collector, negative electrode layer include the negative electrode material that can receive, deviate from lithium ion, and negative electrode material is selected from metal Lithium, lithium alloy, soft carbon, hard carbon, artificial graphite, natural graphite, silicon, silicon oxide compound, silicon-carbon compound, lithium titanate or sulphur.
As a kind of improvement of all solid lithium secondary battery of the present invention, the negative electrode layer with a thickness of 10~200 μm.
As a kind of improvement of all solid lithium secondary battery of the present invention, the negative electrode layer further includes polymer dielectric, leads Electric agent, binder, wherein negative electrode material, polymer dielectric, conductive agent, binder mass ratio be 48~90:8~50:1 ~10:1~10, preferably 60~75:15~30:5:5.
Compared with the existing technology, all solid lithium secondary battery positive plate of the present invention and preparation method thereof and use the anode The all solid lithium secondary battery of piece has the advantages that
1) by after current potential height multi-level recognition, low potential anode layer can consolidate high potential positive electrode with polymer positive plate State electrolyte separates, and the electrochemical oxidation for avoiding polymer dielectric decomposes, and improves the circulation of all solid lithium secondary battery Service life；
2) the high potential anode layer being distributed on plus plate current-collecting body can be improved the energy density of battery；
3) range of choice of copolymer solid electrolyte and the use scope of high potential positive electrode have been widened, has been improved complete The energy density and cyclical stability of solid lithium secondary cell.
Detailed description of the invention
To positive plate of the present invention and preparation method thereof and the positive plate is used below in conjunction with the drawings and specific embodiments All solid lithium secondary battery and its advantages be further elaborated, in which:
Fig. 1 is the structural schematic diagram of all solid lithium secondary battery of the present invention.
Fig. 2 is that all charge and discharge of head of all solid lithium secondary battery progress overcharge test prepared by the embodiment of the present invention 1 are bent Line chart.
Fig. 3 is all charging and discharging curve figures of head that all solid lithium secondary battery prepared by comparative example 1 carries out overcharge test.
Wherein, the reference numerals are as follows:
10 positive plate, 20 negative electrode tab
100 plus plate current-collecting body, 200 negative current collector
102 high potential anode layer, 202 negative electrode layer
104 low potential anode layer, 30 solid polyelectrolyte layer
Specific embodiment
In order to be more clear goal of the invention of the invention, technical solution and its advantageous effects, below in conjunction with attached drawing And specific embodiment, the present invention will be described in further detail.It should be understood that specific reality described in this specification Mode is applied just for the sake of explaining the present invention, is not intended to limit the present invention.
Refering to Figure 1, all solid lithium secondary battery of the present invention includes positive plate 10, negative electrode tab 20 and is interval in anode Solid polyelectrolyte layer 30 between piece 10 and negative electrode tab 20, wherein positive plate 10 by plus plate current-collecting body 100, be coated in Operating potential on plus plate current-collecting body 100 is greater than the high potential anode layer 102 of 3.8V, and is coated in high potential anode layer 102 On operating potential less than or equal to 3.8V low potential anode layer 104 form, negative electrode tab 20 include negative current collector 200 and apply The negative electrode layer 202 being overlying on negative current collector 200.
Refering to Figure 1, the preparation method of all solid lithium secondary battery of the present invention the following steps are included:
1) preparation of positive plate 10:
The preparation of high potential anode layer 102: high potential positive electrode, inorganic solid electrolyte, conductive agent, binder are pressed After the mixing of 48~90:8 of mass ratio~50:1~10:1~10 ratio, suitable organic solvent is added and is mixed and made into slurry, applies It is overlying on 100 surface of plus plate current-collecting body, is compacted after dry, high potential anode layer 102, the preferred aluminium foil of plus plate current-collecting body 100 is made；
The preparation of low potential anode layer 104: low potential positive electrode, inorganic solid electrolyte, conductive agent, binder are pressed After the mixing of 48~90:8 of mass ratio~50:1~10:1~10 ratio, suitable organic solvent is added and is mixed and made into slurry, with Certain thickness ratio is coated on the surface of high potential anode layer 102, forms low potential anode layer 104, dries under a shielding gas Compacting obtains MULTILAYER COMPOSITE positive plate 10 afterwards, and the thickness of low potential anode layer 104 and high potential anode layer 102 is respectively 10~ 200μm。
In anode layer composition, each component content influences whether the building of electronics and lithium ion conducting network in anode layer, if The ratio of positive electrode active materials is higher than 90%, and the content that will lead to solid electrolyte, conductive agent and binder is too low, is unfavorable for electricity The transmitting of son and lithium ion；If the ratio of positive electrode active materials is lower than 50%, the capacity of battery can be reduced, the energy of battery is influenced Density.
2) preparation of solid polyelectrolyte layer 30:
The ratio of polymer body and lithium salts 20~80:80~20 in mass ratio is dissolved in organic solvent respectively and is configured to Polymer dielectric slurry is coated on glass baseplate, and is dried under a shielding gas by polymer dielectric slurry To solid polyelectrolyte layer 30, solid polyelectrolyte layer with a thickness of 5~500 μm；
3) preparation of negative electrode tab 20:
If negative electrode layer 202 selects lithium metal or lithium alloy, lithium metal or lithium alloy are affixed on 200 surface of negative current collector, Negative electrode tab 20 is made；
If negative electrode layer 202 selects nonmetallic lithium or lithium alloy system, by negative electrode material, polymer dielectric, conductive agent, glue After tying the mixing of agent 48~90:8 in mass ratio~50:1~10:1~10 ratio, suitable organic solvent is added and is mixed and made into slurry Material is coated on 200 surface of negative current collector, is compacted after dry in protective gas, negative electrode tab 20 is made；
The preferred copper foil of negative current collector 200, negative electrode layer 202 with a thickness of 10~200 μm；
4) preparation of all solid lithium secondary battery:
The positive plate 10 prepared in step 1) is sliced by required size；
The solid polyelectrolyte layer 30 prepared in step 2) is sliced by required size；
The negative electrode tab 20 prepared in step 3) is sliced by required size；
Positive plate 10 after slice, solid polyelectrolyte layer 30, negative electrode tab 20 are aligned by center and are stacked gradually into Sandwich layer unit；
Sandwich layer unit is combined with each other in 25~150 DEG C of pressurizations, all solid lithium secondary battery battery core is formed, is packaged into All solid lithium secondary battery is obtained after type.
Embodiment 1
1) preparation of positive plate:
The preparation of high potential anode layer: in drying shed, by positive electrode LiCoO2, sulfide solid electrolyte Li3PS4, lead Electric agent VGCF, binder PVDF 70:20:5:5 in mass ratio are mixed in butyl butyrate dicyandiamide solution, are thoroughly mixed uniformly Afterwards, it is coated on aluminium foil surface naturally dry, cold pressing, obtains single layer LiCoO2Anode layer, active layer thickness are 25 μm.
The preparation of low potential anode layer: by positive electrode LiFePO4, sulfide solid electrolyte Li3PS4, conductive agent VGCF, binder PVDF 70:20:5:5 in mass ratio are mixed in butyl butyrate dicyandiamide solution, after being thoroughly mixed uniformly, Coated on LiCoO2Positive layer surface obtains LiCoO through 60 DEG C of drying, cold pressing, slice in protective gas after natural drying2- LiFePO4Anode composite piece, the overall thickness of anode composite layer are 50 μm, LiCoO2Anode layer and LiFePO4The thickness ratio of anode layer For 1:1.
2) preparation of solid polyelectrolyte layer:
By PEO and LiN (CF3SO2)2(being abbreviated as LiTFSI) 100:60 in mass ratio, which is dissolved in tetrahydrofuran (THF), to be prepared At polymer dielectric slurry, it is applied to glass surface and the drying in 60 DEG C of argon atmospheres, dielectric film is obtained, after being sliced Obtain the solid polyelectrolyte layer with a thickness of 50 μm.
3) preparation of negative electrode tab:
Lithium metal is affixed on copper foil surface, is sliced.
4) preparation of all solid lithium secondary battery:
By above-mentioned positive plate, solid polyelectrolyte layer, lithium an- ode piece lamination in order, in 100 DEG C, 250MPa Lower hot pressing 2min obtains battery core unit, and 10 layers of battery core unit hot pressing are placed in outer packing and are encapsulated, and obtains after forming entirely solid State lithium secondary battery.
Embodiment 2
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, high potential is just Pole layer LiCoO2Middle positive electrode LiCoO2、Li3PS4, VGCF, PVDF mass ratio be 48:42:5:5.
Embodiment 3
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, high potential is just Pole layer LiCoO2Middle positive electrode LiCoO2、Li3PS4, VGCF, PVDF mass ratio be 70:20:1:9.
Embodiment 4
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, high potential is just Pole layer LiCoO2Middle positive electrode LiCoO2、Li3PS4, VGCF, PVDF mass ratio be 90:8:1:1.
Embodiment 5
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, LiFePO4Just Pole layer with a thickness of 10 μm, LiCoO2Anode layer with a thickness of 10 μm.
Embodiment 6
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, LiFePO4Just Pole layer with a thickness of 10 μm, LiCoO2Anode layer with a thickness of 200 μm.
Embodiment 7
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, LiFePO4Just Pole layer with a thickness of 200 μm, LiCoO2Anode layer with a thickness of 200 μm.
Embodiment 8
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, low potential is just The positive electrode of pole layer is FePO4, the positive electrode of high potential anode layer is LiNi0.6Co0.2Mn0.2O2。
Embodiment 9
Essentially identical with the preparation method of embodiment 8, difference is: solid polyelectrolyte layer with a thickness of 10 μ m。
Embodiment 10
Essentially identical with the preparation method of embodiment 8, difference is: solid polyelectrolyte layer with a thickness of 200 μ m。
Embodiment 11
Essentially identical with the preparation method of embodiment 8, difference is: solid polyelectrolyte layer with a thickness of 500 μ m。
Embodiment 12
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, low potential is just The positive electrode of pole layer is Li7Ti5O12, the positive electrode of high potential anode layer is LiNi0.5Mn1.5O2。
Embodiment 13
Essentially identical with the preparation method of embodiment 12, difference is: lithium salts in solid polyelectrolyte layer component For Li3PS4。
Embodiment 14
Essentially identical with the preparation method of embodiment 12, difference is: lithium salts in solid polyelectrolyte layer component For Li10GeP2S12(being abbreviated as LGPS).
Embodiment 15
Essentially identical with the preparation method of embodiment 12, difference is: polymerizeing in solid polyelectrolyte layer component Object ontology is PAN.
Embodiment 16
Essentially identical with the preparation method of embodiment 1, difference is:
In the preparation process of positive plate, the positive electrode of low potential anode layer is Li1.5V2O5, high potential anode layer is just Pole material is LiCoPO4。
In the preparation process of negative electrode tab, lithium an- ode is replaced by graphite cathode, the preparation method comprises the following steps: in drying shed, it will Graphite, sulfide solid electrolyte Li3PS4, binder PVDF 70:25:5 in mass ratio, be mixed in N-Methyl pyrrolidone (NMP) in dicyandiamide solution, after being thoroughly mixed uniformly, it is coated on copper foil surface, after natural drying through 60 in protective gas DEG C drying, cold pressing, slice, obtain the graphite cathode that thickness is about 50 μm.
Embodiment 17
Essentially identical with the preparation method of embodiment 16, difference is: applying in all solid lithium secondary battery preparation process Pressure pressure is 20MPa, and pressure temperature is 25 DEG C.
Embodiment 18
Essentially identical with the preparation method of embodiment 16, difference is: applying in all solid lithium secondary battery preparation process Pressure pressure is 20MPa.
Embodiment 19
Essentially identical with the preparation method of embodiment 16, difference is: applying in all solid lithium secondary battery preparation process Pressure pressure is 500MPa, and pressure temperature is 25 DEG C.
Embodiment 20
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, high potential is just The positive electrode of pole layer is LiCoO2With LiNi0.6Co0.2Mn0.2O2Mixture, LiCoO2With LiNi0.6Co0.2Mn0.2O2Matter Amount is than being 1:1.
Embodiment 21
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, low potential is just The positive electrode of pole layer is LiFePO4With Li7Ti5O12Mixture, LiFePO4With Li7Ti5O12Mass ratio be 1:1.
Embodiment 22
Essentially identical with the preparation method of embodiment 1, difference is: in the preparation process of positive plate, high potential is just The positive electrode of pole layer is LiCoO2With LiNi0.6Co0.2Mn0.2O2Mixture, LiCoO2With LiNi0.6Co0.2Mn0.2O2Use Amount ratio is 1:1.The positive electrode of low potential anode layer is LiFePO4With Li7Ti5O12Mixture, LiFePO4With Li7Ti5O12Mass ratio be 1:1.
Comparative example 1
The preparation of positive plate: in drying shed, by positive electrode LiFePO4, sulfide solid electrolyte Li3PS4, conductive agent VGCF, binder PVDF 70:20:5:5 in mass ratio are mixed in N-Methyl pyrrolidone (NMP) dicyandiamide solution, are sufficiently stirred After mixing, it is coated on aluminium foil surface naturally dry, cold pressing, obtains LiFePO4Positive lamella, positive lamella with a thickness of 50 μm。
The preparation of solid polyelectrolyte layer: with embodiment 1.
The preparation of lithium an- ode piece: with embodiment 1.
The preparation of all solid lithium secondary battery: with embodiment 1.
Comparative example 2
The preparation of positive plate: preparation process is with comparative example 1, except that the positive electrode used is LiCoO2。
The preparation of solid polyelectrolyte layer: with embodiment 1.
The preparation of lithium an- ode piece: with embodiment 1.
The preparation of all solid lithium secondary battery: with embodiment 1.
Comparative example 3
The preparation of positive plate: preparation process is with comparative example 1, except that the positive electrode used is LiNi0.6Co0.2Mn0.2O2。
Solid polyelectrolyte layer preparation: with embodiment 1.
The preparation of lithium an- ode piece: with embodiment 1.
The preparation of all solid lithium secondary battery: with embodiment 1.
The design parameter of Examples 1 to 22 and comparative example 1~3 is as shown in table 1.
The design parameter of 1 embodiment and comparative example of table is arranged
All solid lithium secondary battery progress charge-discharge performance test process is set in above-described embodiment 1~11 and comparative example 2~3 Set as follows: operating voltage range is set as 2.8V~4.2V, and loop test is carried out by the way of constant current charge-discharge, wherein surveys Examination electric current is that (current density is about 0.13mA/cm to 0.1C2), test temperature is 70 DEG C.
All solid lithium secondary battery carries out charge-discharge performance test process and is provided that operating voltage in embodiment 12~22 Range is set as 2.8V~5.0V, and loop test is carried out by the way of constant current charge-discharge, wherein test electric current is 0.1C (electricity Current density is about 0.13mA/cm2), test temperature is 70 DEG C.
All solid lithium secondary battery carries out charge-discharge performance test process and is provided that operating voltage range in comparative example 1 It is set as 2.8V~3.8V, loop test is carried out by the way of constant current charge-discharge, wherein test electric current is that (electric current is close by 0.1C Degree is about 0.13mA/cm2), test temperature is 70 DEG C.
The all solid lithium secondary battery of Examples 1 to 22 and comparative example 1~3 test battery all specific discharge capacities of head, First week coulombic efficiency, the capacity retention ratio of energy density and circulation after 50 weeks, 200 weeks, experimental result are as shown in table 2.
The performance test results of all solid lithium secondary battery of 2 Examples 1 to 22 of table and comparative example 1~3
By Examples 1 to 22 and comparative example 1~3 it is found that polymer dielectric and positive material in all solid lithium secondary battery The compatibility of material determines the chemical property of battery.The solid polyelectrolytes such as PEO and LiFePO4Equal low potentials anode material Expect that compatibility is good, therefore (Fig. 2 show the charge and discharge of embodiment 1 to battery discharge specific capacity height in Examples 1 to 22 and comparative example 1 Electric curve graph, Fig. 3 show the charging and discharging curve figure of comparative example 1).In battery the solid polyelectrolytes such as PEO layer directly with (LiCoO in such as comparative example 2 when high potential positive electrode contacts2Or LiNi in comparative example 30.6Co0.2Mn0.2O2Deng), charging process Middle PEO is persistently oxidized, and battery is caused to be difficult to charge normal (comparative example 2~3).
By embodiment 1 and comparative example 1 it is found that in the comparable situation of cell positive material dosage, due to making in embodiment 1 With the LiFePO of positive electrode containing low potential4With high potential positive electrode LiCoO2Anode composite piece, electric discharge with higher is flat Platform, so that the energy density of battery is apparently higher than the single LiFePO in comparison 1 in embodiment 14System.
By Examples 1 to 4 it is found that with positive electrode in low potential and high potential anode layer and electrolyte content ratio Difference, battery show all specific discharge capacities of different head, energy density and cyclical stability.Wherein, positive electrode content ratio When example is 70% (embodiment 1), battery shows all specific capacities of good head and first all coulombic efficiencies.Positive electrode content mistake Low (48%, embodiment 2), positive electrode content excessively high (90%, embodiment 4), inorganic solid electrolyte content it is too low (8%, it is real Apply example 4), conductive agent content too low (1%, embodiment 3~4), binder content too low (1%, embodiment 4) etc., will lead to Battery discharge specific capacity is substantially reduced, energy density reduces and cyclical stability reduces.This is because positive material in battery pole piece The difference of material, solid electrolyte, conductive agent, binder equal size can cause electronics and ionic conduction network in electrode plates Difference, and then cause the difference of battery performance.
By embodiment 1 and 5~7 it is found that high potential/low potential anode layer thickness can shadow than the thickness of, anode composite layer Ring the performance of battery.When the thickness of high potential anode layer is larger (embodiment 6~7), all energy densities of the head of battery obviously increase Greatly, it is easy to cause lithium ion conduction in positive plate difficult when but positive plate thickness is larger, battery polarization increases, and further results in Battery specific discharge capacity in cyclic process persistently reduces and capacity attenuation accelerates (embodiment 6~7).When high potential anode layer When thickness is smaller (embodiment 5), there is battery preferable electronics and ion network is connected, and have preferably battery capacity and circulation Stability.
By embodiment 8~11 it is found that the thickness of solid polyelectrolyte layer also has biggish shadow to battery performance performance It rings.Since the conductivity of solid polyelectrolyte layer is lower, the increase of the thickness of electrolyte layer can not only cause battery compared with Big polarization reduces the specific capacity of battery, and can reduce the energy density of battery.But solid polyelectrolyte layer When thickness is less than 10 μm, electrolyte layer is easy to be pierced through by lithium, causes battery short circuit (embodiment 9).
By embodiment 12~15 it is found that changing polymer body in solid polyelectrolyte layer, the type of lithium salts also can Influence battery performance.Use the higher Li of conductivity3PS4Instead of LiTFSI, helps to improve the first all specific discharge capacities of battery, follows Ring performance etc., but after introducing the LGPS of reducing resistance difference, since reduction reaction persistently occurs in battery charging process for LGPS, Battery performance can be deteriorated.In addition, polymer body material will affect the conductivity of electrolyte layer, PAN replaces PEO post-consumer polymer electricity The conductivity for solving matter layer reduces, and battery polarization increases, and causes cell performance decay.
By embodiment 16~19 it is found that all solid lithium secondary battery molding pressure pressure and temperature also has shadow to battery performance It rings.When the pressure and temperature that presses is too low (embodiment 17), the conducting network of lithium ion and electronics is poor in battery pole lamella, battery pole Change obviously, battery shows extremely low specific discharge capacity and cycle performance.The promotion molding pressure of battery (embodiment 16,19), Temperature (embodiment 16,18) can improve battery performance, but when battery briquetting pressure is excessive (embodiment 19), pole piece toughness compared with Difference easily occurs the fracture of the pole piece as caused by the volume expansion of positive and negative pole material in battery charge and discharge process, and then causes The continuous decrement of cycle performance of battery.
By embodiment 20~22 it is found that when high potential anode layer and low potential anode layer use composite positive pole, battery Also it can express good chemical property.
It is secondary to improve all solid lithium it is found that after using low potential/high potential anode composite piece for integrated embodiment 1~22 Compatibility in battery between polymer dielectric and positive electrode has widened polymer dielectric, the positive electrode and negative electrode of battery The selectivity of material.
It can be seen that compared with the existing technology in conjunction with the test result of above embodiments and comparative example, the present invention is all solid state The all solid lithium secondary battery of cathode plate for lithium secondary battery piece and preparation method thereof and use positive plate has below beneficial to effect Fruit:
1) positive plate is by after current potential height multi-level recognition, and low potential anode layer 104 is by high potential positive electrode and polymer Solid electrolyte separates, and the electrochemical oxidation for avoiding polymer dielectric decomposes, and improves following for all solid lithium secondary battery The ring service life；
2) the high potential anode layer 102 being distributed on plus plate current-collecting body can be improved the energy density of battery；
3) range of choice of copolymer solid electrolyte and the use scope of high potential positive electrode have been widened, has been improved complete The energy density and cyclical stability of solid lithium secondary cell.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.

Claims (12)

1. a kind of positive plate, it is characterised in that: the positive plate includes plus plate current-collecting body and is distributed in answering on plus plate current-collecting body Anode layer is closed, anode composite layer is greater than the high potential anode layer and distribution of 3.8V by the operating potential being distributed on plus plate current-collecting body It is formed in low potential anode layer of the operating potential in high potential anode layer less than or equal to 3.8V.
2. positive plate according to claim 1, it is characterised in that: the thickness of the high potential anode layer and low potential anode layer Degree is respectively 10~200 μm.
3. positive plate according to claim 1, it is characterised in that: the high potential anode layer contains high potential anode material Material, inorganic solid electrolyte, conductive agent and binder, wherein high potential positive electrode, conductive agent, glues inorganic solid electrolyte The mass ratio for tying agent is 48~90:8~50:1~10:1~10, preferably 60~75:15~30:5:5.
4. positive plate according to claim 3, it is characterised in that: the high potential positive electrode is selected from Layered Lithium metal oxygen Compound, spinel structure lithium metal oxide, lithium metal phosphates, lithium metal fluorination sulfate, lithium metal vanadate and right Layered lithium metal oxides, spinel structure lithium metal oxide, lithium metal phosphates, lithium metal are fluorinated sulfate, lithium metal At least one of modified material of vanadate.
5. positive plate according to claim 4, it is characterised in that: layered lithium metal oxide is selected from cobalt acid lithium LiCoO2, lithium nickelate LiNiO2, ternary material LiNimBnC(1-m-n)O2At least one of, wherein B, C be respectively selected from Co, Al, At least one of Mn, and B and C be not identical, 0 < m < 1,0 < n < 1；The spinel structure lithium metal compounds are selected from LiMn2O4 LiMn2O4And/or nickel ion doped LiNi0.5Mn1.5O4；The lithium metal phosphates are selected from cobalt phosphate lithium LiCoPO4And/or phosphoric acid Nickel lithium LiNiPO4；The lithium metal fluorination sulfate is selected from fluorination cobaltous sulfate lithium LiCoFSO4；The lithium metal vanadate is selected from Vanadic acid nickel lithium LiNiVO4；The modified material is selected to layered lithium metal oxides, spinel structure lithium metal oxide, lithium Metal phosphate, lithium metal fluorination sulfate or lithium metal vanadic acid salt dopping and cladding treated material, doping and cladding Element is selected from least one of Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W.
6. positive plate according to claim 1, it is characterised in that: the low potential anode layer contains low potential anode material Material, inorganic solid electrolyte, conductive agent and binder, wherein low potential positive electrode, inorganic solid electrolyte, conductive agent and The mass ratio of binder is 48~90:8~50:1~10:1~10, preferably 60~75:15~30:5:5.
7. positive plate according to claim 6, it is characterised in that: the low potential positive electrode is selected from LiFePO4, phosphorus At least one of sour iron, lithium titanate, vanadic anhydride, metal sulfide, thiophosphate.
8. positive plate according to claim 7, it is characterised in that: the metal sulfide is selected from CuS2、FeS2、MoS2、 NiS、TiS2At least one of；The thiophosphate is selected from Li2FeP2S6And/or LiTi2(PS4)3。
9. a kind of method for preparing positive plate according to any one of claims 1 to 8, which comprises the following steps:
1) positive electrode of high potential anode layer, inorganic solid electrolyte, conductive agent, binder are mixed with certain mass ratio Afterwards, suitable organic solvent is added and is mixed and made into slurry, is coated on collector plus plate current-collecting body surface, is compacted, is made after dry High potential anode layer；
2) positive electrode of low potential anode layer, inorganic solid electrolyte, conductive agent, binder are mixed with certain mass ratio Afterwards, suitable organic solvent is added and is mixed and made into slurry, high potential anode layer surface is coated on certain thickness ratio, is formed low Potential cathode layer is compacted obtain anode composite piece after dry in protective gas.
10. the preparation method of positive plate according to claim 9, which is characterized in that in the step 1) and step 2) just Pole material, inorganic solid electrolyte, conductive agent, binder mass ratio be 48~90:8~50:1~10:1~10, preferably 60 ~75:15~30:5:5.
11. the preparation method of positive plate according to claim 9, which is characterized in that the protective gas is nitrogen or lazy Property gas, compaction pressure be 20~500MPa, preferably 200~300MPa, compacted density be 1.8~4.2g/cm3, compacting temperature It is 25~150 DEG C.
12. a kind of all solid lithium secondary battery, including positive plate, negative electrode tab and the polymerization being interval between positive plate and negative electrode tab Object solid-state electrolyte layer, it is characterised in that: the positive plate is positive plate described in any item of the claim 1 to 8.
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CN113113568A (en) * 2020-08-07 2021-07-13 昆山宝创新能源科技有限公司 Negative electrode with gradient potential distribution, lithium ion battery and preparation method and application thereof
CN111952661A (en) * 2020-08-14 2020-11-17 横店集团东磁股份有限公司 Solid-state lithium ion battery and preparation method thereof
CN113410433A (en) * 2021-06-16 2021-09-17 昆山宝创新能源科技有限公司 Gradient potential distribution composite electrode, preparation method thereof and power battery

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