CN108963205A - A kind of solid state lithium battery of NEW TYPE OF COMPOSITE anode and its preparation method and application - Google Patents

A kind of solid state lithium battery of NEW TYPE OF COMPOSITE anode and its preparation method and application Download PDF

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Publication number
CN108963205A
CN108963205A CN201810601269.3A CN201810601269A CN108963205A CN 108963205 A CN108963205 A CN 108963205A CN 201810601269 A CN201810601269 A CN 201810601269A CN 108963205 A CN108963205 A CN 108963205A
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composite
solid electrolyte
anode
lithium
weight percent
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孟繁慧
郑涛
马洪运
王欣全
周江
伍绍中
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Tianjin Lishen Battery JSCL
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Tianjin Lishen Battery JSCL
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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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/50—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
    • 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
    • H01M4/52—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
    • 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
    • H01M4/58—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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

Abstract

The preparation method of a kind of NEW TYPE OF COMPOSITE anode disclosed by the invention, comprising steps of step 1: preparing composite solid electrolyte solution；Step 2: carrying out compounding mixing according to preset ratio, and stir evenly, and be coated on plus plate current-collecting body, then drying, prepare anode composite composite solid electrolyte solution, positive electrode active materials, conductive agent and dispersing agent；Step 3: composite solid electrolyte solution prepared by the first step, is coated on the anode composite again, then dries, it is final to obtain the anode composite for having compounded composite solid electrolyte.In addition, the invention also discloses a kind of NEW TYPE OF COMPOSITE anode and its solid state lithium batteries of application.The present invention can guarantee between solid electrolyte and electrode active material and solid electrolyte and battery electrode it is soft contact, reduce the interface impedance between solid electrolyte and electrode active material and solid electrolyte and battery electrode.

Description

A kind of solid state lithium battery of NEW TYPE OF COMPOSITE anode and its preparation method and application
Technical field
The present invention relates to battery technology fields, more particularly to a kind of NEW TYPE OF COMPOSITE anode and its preparation method and application Solid state lithium battery.
Background technique
Currently, lithium ion battery have many advantages, such as specific energy is high, be recycled often, storage time it is long, not only just It takes such as mobile phone, DV and laptop computer on formula electronic equipment to be used widely, and is widely used in electricity In terms of the large and medium-sized electrical equipment such as electrical automobile, electric bicycle and electric tool, therefore, not in view of lithium ion battery applications It is disconnected to expand, so that demand of the market to lithium ion battery energy density is being continuously improved, meanwhile, so as to the peace of lithium ion battery Full performance requirement is higher and higher.
Currently, the intrinsic essential safety attribute of solid state lithium battery, receives significant attention it.On the one hand, traditional lithium from There are the security risks that leakage, easy catching fire even explode for sub- battery, therefore, boiling point height and nonflammable solid state electrolysis Matter becomes the important technology selection for solving lithium ion battery safety problem.On the other hand, the chemical inertness of solid electrolyte is utilized And high-intensitive mechanical characteristics, inside battery side reaction can be inhibited to occur and Li dendrite is inhibited to be formed, and then optimize and promote lithium electricity The application that the safety in pond is lithium metal in lithium ion battery provides solution.
Solid electrolyte is the key technology of solid lithium battery.Solid electrolyte mainly includes oxide, sulfide, gathers Close object and hybrid solid-state electrolyte.Wherein, elasticity is good, easily film forming, machining property is good for polymer dielectric, is easy to work Industryization preparation, still, lower conductivity at room temperature restricts the large-scale application of polymer dielectric always.
Therefore, there is an urgent need to develop a kind of technologies out at present, can effectively promote the ion-conductance that solid electrolyte has Conductance, thus guarantee between solid electrolyte and electrode active material and solid electrolyte and battery electrode it is soft contact, reduce Interface impedance between solid electrolyte and battery electrode.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of solid-state lithiums of NEW TYPE OF COMPOSITE anode and its preparation method and application Battery, the ionic conductivity having by effectively promoting solid electrolyte, to guarantee solid electrolyte and electrode activity material Soft between material and solid electrolyte and battery electrode contacts, and reduces solid electrolyte and electrode active material and solid state electrolysis Interface impedance between matter and battery electrode is conducive to widely production application, is of great practical significance.
For this purpose, the present invention provides a kind of NEW TYPE OF COMPOSITE anode, including composite solid electrolyte, positive electrode active materials, lead Electric agent and dispersing agent, in which:
The weight percent that the composite solid electrolyte accounts for the anode composite is 1~30%；
The weight percent that the positive electrode active materials account for the anode composite is 50~98%；
The weight percent that the conductive agent accounts for the anode composite is 1~20%；
The weight percent that the dispersing agent accounts for the anode composite is 0~5%.
Wherein, it is 2~20% that the composite solid electrolyte, which accounts for the weight percent of the anode composite,；
The weight percent that the positive electrode active materials account for the anode composite is 70~96%；
The weight percent that the conductive agent accounts for the anode composite is 2~10%；
The weight percent that the dispersing agent accounts for the anode composite is 0~3%；
The composite solid electrolyte include weight percent be 10%~90% solid polyelectrolyte, 1%~ 60% oxidation silicon substrate framework structured compound and 1%~60% ionic liquid.
Wherein, the solid polyelectrolyte includes the lithium salts and 50%~95% that weight percent is 5%~50% Polymer；
Cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, quaternary ammonium salt He quaternary phosphine One of salt, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluoro-phosphate radical [PF6]-, trifluoro Sulfonyl methane imines root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-, nitrate anion [NO3]-, bromide ion Br-With chloride ion Cl-One of described in positive electrode active materials include cobalt acid lithium LiCoO2, nickle cobalt lithium manganate Ternary material NCM, LiFePO4 LiFePO4, lithium manganese phosphate LiMnPO4With vanadium phosphate LiVPO4At least one of；
The conductive agent includes that black carbon black, krypton cyanogen, active carbon, carbon nanotube CNT, graphene Graphene and graphite-like are led At least one of electric agent；
The dispersing agent is polyvinylpyrrolidone PVP.
Wherein, the polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), polyvinyl chloride PPC, polyethylene glycol oxide At least one of PEO modified structure and polyacrylonitrile (PAN) modified structure；
The lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4 With hexafluoroarsenate lithium LiAsF6At least one of.
In addition, the present invention also provides a kind of solid state lithium battery, including foregoing NEW TYPE OF COMPOSITE anode, composite solid Electrolyte layer and battery cathode；
The composite solid electrolyte layer is between the NEW TYPE OF COMPOSITE Anode and battery cathode.
In addition, the present invention also provides a kind of preparation methods of NEW TYPE OF COMPOSITE anode, comprising the following steps:
Step 1: preparing composite solid electrolyte solution；
Step 2: by composite solid electrolyte solution, positive electrode active materials, conductive agent and dispersing agent, according to preset ratio Example carries out compounding mixing, and stirs evenly, and be coated on plus plate current-collecting body, then dries, prepares anode composite；
Step 3: composite solid electrolyte solution prepared by the first step, is coated on the anode composite, then again Drying, it is final to obtain the anode composite for having compounded composite solid electrolyte.
Wherein, the quality in second step, between composite solid electrolyte, positive electrode active materials, conductive agent and dispersing agent Than for 5:85:8:2 or 10:85:4:1；
The positive electrode active materials include cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material NCM, LiFePO4 LiFePO4, lithium manganese phosphate LiMnPO4With vanadium phosphate LiVPO4At least one of；
The conductive agent includes that black carbon black, krypton cyanogen, active carbon, carbon nanotube CNT, graphene Graphene and graphite-like are led At least one of electric agent；
The dispersing agent is polyvinylpyrrolidone PVP.
Wherein, in second step, specific drying operation are as follows: be initially positioned in dry atmosphere and dry, drying temperature be 40~ 130 DEG C, drying time is 0~20 hour, is then placed in vacuum tank again and carries out secondary drying, and drying temperature is 40~130 DEG C, drying time is 0~60 hour.
Wherein, in the third step, the anode composite for being coated with composite solid electrolyte solution is placed in dry gas first It is dried in atmosphere, drying temperature is 40~130 DEG C, and drying time is 0~20 hour, is then placed in vacuum tank and is dried again Dry, drying temperature is 40~130 DEG C, and drying time is 0~60 hour.
Wherein, the first step specifically includes the following steps:
Polymer and lithium salts are dissolved in preset solvent by the first sub-step, are configured to solid polyelectrolyte solution, Wherein polymer and lithium salts form solid polyelectrolyte together；
Second sub-step, tetraethyl orthosilicate is dissolved in formic acid, is then mixed with ionic liquid, be configured to by from First mixed solution of sub- liquid, tetraethyl orthosilicate and formic acid composition；
Third sub-step: solid polyelectrolyte solution and the first mixed solution are mixed according to preset quality ratio It closes, stirs evenly and obtain composite solid electrolyte solution；
In the first sub-step, the preset solvent is tetrahydrofuran；
In the first sub-step, the solid content of the solid polyelectrolyte solution is 1%~50%, and compound In the solid content of solid electrolyte, the weight ratio between polymer and lithium salts is (1:1)~(95:5)；
The polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, polyethylene glycol oxide PEO At least one of modified structure and polyacrylonitrile (PAN) modified structure；
The lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4 With hexafluoroarsenate lithium LiAsF6At least one of；
In the second sub-step, in first mixed solution, the weight percent of ionic liquid is 1%~30%, The weight percent of tetraethyl orthosilicate is 1%~20%, and the weight percent of formic acid is 50%~98%；
Cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, quaternary ammonium salt He quaternary phosphine One of salt, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluoro-phosphate radical [PF6]-, trifluoro Sulfonyl methane imines root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-, nitrate anion [NO3]-, bromide ion Br-With chloride ion Cl-One of；
In third sub-step, the preset mass ratio is 1:1.
By the above technical solution provided by the invention as it can be seen that compared with prior art, the present invention provides a kind of novel The solid state lithium battery of anode composite and its preparation method and application, the ionic conductance having by effectively promoting solid electrolyte Rate, thus guarantee between solid electrolyte and electrode active material and solid electrolyte and battery electrode it is soft contact, reduce solid Interface impedance between state electrolyte and electrode active material and solid electrolyte and battery electrode is conducive to widely produce and answer With being of great practical significance.
By applying the anode composite provided by the invention based on NEW TYPE OF COMPOSITE solid electrolyte, may be implemented using solid-state Electrolyte and the electrolyte and combination electrode of electrode active material and solid electrolyte and interelectrode soft contact are battery pack Part advantageously reduces the solid state lithium battery finally prepared so as to further prepare the solid state lithium battery of low impedance structure Impedance is advantageously implemented the large-scale application of solid state lithium battery.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method of NEW TYPE OF COMPOSITE anode provided by the invention；
Fig. 2 is the preparation method with the anode composite provided by the invention based on NEW TYPE OF COMPOSITE solid electrolyte, in reality The oxidizing potential test based on NEW TYPE OF COMPOSITE solid electrolyte and existing polyethylene glycol oxide PEO electrolyte for applying the preparation of example 1 is bent Line contrast schematic diagram, wherein A curve indicates that polyethylene glycol oxide PEO, B curve indicate composite solid electrolyte provided by the invention.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, with reference to the accompanying drawing with embodiment to this Invention is described in further detail.
The present invention provides a kind of NEW TYPE OF COMPOSITE anode, comprising composite solid electrolyte, positive electrode active materials, conductive agent and Dispersing agent, in which:
The weight percent that the composite solid electrolyte accounts for the anode composite is 1~30%, preferably 2~20%；
The positive electrode active materials account for the anode composite weight percent be 50-98%, preferably 70~96%；
The weight percent that the conductive agent accounts for the anode composite is 1~20%, preferably 2~10%；
The weight percent that the dispersing agent accounts for the anode composite is 0~5%, preferably 0~3%；
In the present invention, in specific implementation, the composite solid electrolyte includes that weight percent is 10%~90% Solid polyelectrolyte, 1%~60% oxidation silicon substrate framework structured compound and 1%~60% ionic liquid.
In the present invention, in specific implementation, the solid polyelectrolyte includes that weight percent is 5%~50% Lithium salts and 50%~95% polymer.
In specific implementation, the polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, gathers At least one of ethylene oxide PEO modified structure and polyacrylonitrile (PAN) modified structure.
In specific implementation, the lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, four Lithium fluoroborate LiBF4With hexafluoroarsenate lithium LiAsF6At least one of.
In the present invention, in specific implementation, the cation in the ionic liquid include alkyl-substituted pyrroles, thiazole, Piperidines, imidazoles, quaternary ammonium salt He one of quaternary alkylphosphonium salt, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-、 Hexafluoro-phosphate radical [PF6]-, trifluoromethanesulfonimide root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoro boron Acid group [BF4]-, nitrate anion [NO3]-, bromide ion Br-With chloride ion Cl-One of.
It should be noted that for the present invention, the composite solid electrolyte provided, be by solid polyelectrolyte, Aoxidize silicon substrate framework structured compound and ionic liquid composition.
Wherein, solid polyelectrolyte aoxidizes silicon substrate skeleton structure for constructing main structure and transmitting lithium ion The fluid dynamics that object is used to carry and limit ionic liquid are closed, ionic liquid and oxidation silicon substrate framework structured compound are for filling out It fills in solid polyelectrolyte main structure, solid electrolyte and active material and the lithium ion finally prepared may be implemented The interelectrode soft contact of battery, to reduce the boundary between active material, between the electrode and solid electrolyte of lithium ion battery Face impedance.
It should be noted that oxidation silicon substrate framework structured compound: being obtained especially by the method for collosol and gel, i.e., former silicon Sour tetra-ethyl ester heats generation hydrolysis in formic acid solution, condensation reaction generates silica skeleton structure.The silica skeleton structure Liquefied compound can be carried, gel is formed.Herein similarly to the prior art, description is not further spread out.
In the present invention, in specific implementation, the positive electrode active materials include for cobalt acid lithium LiCoO2, nickle cobalt lithium manganate three First material NCM, LiFePO4 LiFePO4, lithium manganese phosphate LiMnPO4With vanadium phosphate LiVPO4At least one of.
In the present invention, in specific implementation, the conductive agent includes that carbon black, krypton cyanogen is black, active carbon, carbon nanotube CNT, stone At least one of black alkene Graphene and graphite-like conductive agent；
In the present invention, in specific implementation, the dispersing agent is polyvinylpyrrolidone PVP.
It, can be with by applying the anode composite based on NEW TYPE OF COMPOSITE solid electrolyte it should be noted that for the present invention It cooperates with the battery cathode for the protective layer for being coated with LiPON LiPON, polyethylene glycol oxide PEO or oxide on surface, By the way that anode composite, composite solid electrolyte layer, battery cathode are superimposed, acquisition solid state lithium battery can be made.
Based on the NEW TYPE OF COMPOSITE anode that aforementioned present invention provides, the present invention also provides a kind of solid state lithium batteries, including multiple The anode composite, composite solid electrolyte layer and battery cathode of composite solid electrolyte are matched；
It is (i.e. noted earlier that the composite solid electrolyte layer is located at the anode composite for having compounded composite solid electrolyte Combined electrode) and battery cathode between.
In the present invention, in specific implementation, the battery cathode is preferably wrapped on aluminium foil (as negative current collector) surface It is covered with the battery cathode of the protective layer of LiPON LiPON, polyethylene glycol oxide PEO or oxide.
It should be noted that composite solid electrolyte layer, plays the role of diaphragm, and be conducive to the conduction of lithium ion. Composite solid electrolyte layer is one layer of intermediate interlayer being made of composite solid electrolyte, electric positioned at composite solid has been compounded Between the anode composite and battery cathode for solving matter.
In addition, shown in Figure 1, the present invention also provides a kind of preparation methods of NEW TYPE OF COMPOSITE anode, are used to prepare State NEW TYPE OF COMPOSITE provided by the invention anode, can be used in specifically preparing solid state lithium battery, this method specifically includes the following steps:
Step 1: preparing composite solid electrolyte solution；
Step 2: by composite solid electrolyte solution, positive electrode active materials, conductive agent and dispersing agent, according to preset ratio Example carries out compounding mixing, and stirs evenly, and be coated on plus plate current-collecting body, then dries, prepares anode composite；
In second step, the plus plate current-collecting body can be aluminium foil.
In the present invention, in second step, the conductive agent includes that carbon black, krypton cyanogen is black, active carbon, carbon nanotube CNT, stone At least one of black alkene Graphene and graphite-like conductive agent；
In the present invention, in specific implementation, the dispersing agent is polyvinylpyrrolidone PVP.
Step 3: composite solid electrolyte solution prepared by the first step, is coated on the anode composite, then again Drying, it is final to obtain the anode composite for having compounded composite solid electrolyte.
In second step, composite solid electrolyte (solid content when no formic acid), positive electrode active materials, conductive agent and point Mass ratio between powder is 5:85:8:2 or 10:85:4:1.
In second step, specific drying operation are as follows: it is initially positioned in dry atmosphere and dries, drying temperature is 40~130 DEG C, Drying time is 0~20 hour, is then placed in vacuum tank again and carries out secondary drying, and drying temperature is 40~130 DEG C, drying Time is 0~60 hour.
In the third step, the anode composite for being coated with composite solid electrolyte solution is placed in dry atmosphere first and is dried Dry, drying temperature is 40~130 DEG C, and drying time is 0~20 hour, is then placed in vacuum tank and is dried again, is dried Temperature is 40~130 DEG C, and drying time is 0~60 hour.
For the present invention, it should be noted that for having compounded the anode composite of composite solid electrolyte, wherein compound Composite solid electrolyte can play the role of diaphragm and be conducive to the conduction of lithium ion simultaneously when assembling solid lithium battery.
In the present invention, in specific implementation, the positive electrode active materials may include cobalt acid lithium LiCoO2, nickle cobalt lithium manganate Ternary material NCM, LiFePO4 LiFePO4, lithium manganese phosphate LiMnPO4With vanadium phosphate LiVPO4At least one of.
It should be noted that after preparing and having compounded the anode composite of composite solid electrolyte, can also and surface The battery cathode of protective layer containing LiPON LiPON, polyethylene glycol oxide PEO or oxide cooperates, and passes through routine The assembly method of solid state lithium battery assembles solid state lithium battery.
For the present invention, the first step specifically includes the following steps:
Polymer and lithium salts are dissolved in preset solvent by the first sub-step, are configured to solid polyelectrolyte solution, Wherein polymer and lithium salts form solid polyelectrolyte together；
Second sub-step, tetraethyl orthosilicate is dissolved in formic acid, is then mixed with ionic liquid, be configured to by from First mixed solution of sub- liquid, tetraethyl orthosilicate and formic acid composition；
Third sub-step: solid polyelectrolyte solution and the first mixed solution are mixed according to preset quality ratio It closes, stirs evenly and obtain composite solid electrolyte solution.
In the present invention, in specific implementation, in the first sub-step, the preset solvent is tetrahydrofuran.
In the present invention, in specific implementation, in the first sub-step, the solid content of the solid polyelectrolyte solution (weight) is 1%~50%, and in the solid content of composite solid electrolyte, the weight ratio between polymer and lithium salts is (1:1)~(95:5).
In specific implementation, the polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, gathers At least one of ethylene oxide PEO modified structure and polyacrylonitrile (PAN) modified structure.
In specific implementation, the lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, four Lithium fluoroborate LiBF4With hexafluoroarsenate lithium LiAsF6At least one of.
In the present invention, in the second sub-step, in first mixed solution, the weight percent of ionic liquid is 1%~30%, the weight percent of tetraethyl orthosilicate is 1%~20%, and the weight percent of formic acid is 50%~98%.
In specific implementation, the cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, season One of ammonium salt He quaternary alkylphosphonium salt, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluoro-phosphate radical [PF6]-, trifluoromethanesulfonimide root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-、 Nitrate anion [NO3]-, bromide ion Br-With chloride ion Cl-One of.
In the present invention, in third sub-step, the preset mass ratio is 1:1.
Below with reference to embodiment 1 to embodiment 2, illustrate that the one kind provided according to the present invention is based on NEW TYPE OF COMPOSITE solid state electrolysis The preparation method of the anode composite of matter produces the detailed process of the anode composite based on NEW TYPE OF COMPOSITE solid electrolyte.
Embodiment 1
In specific embodiment 1, the present invention prepares the anode composite based on NEW TYPE OF COMPOSITE solid electrolyte, including following step It is rapid:
Step 1: firstly, the lithium salts LiTFSI of the polymer P EO (400,000 molecular weight) of 5g, 5g is taken to be dissolved in the solvent four of 90g In hydrogen furans, be configured to solid polyelectrolyte solution, weight percentage: polymer P EO is 5%, and lithium salts LiTFSI is 5%；Then, it takes the tetraethyl orthosilicate of 10g to be dissolved in 80g formic acid, and mixes the ionic liquid of 10g, the solion is specific Are as follows: bis- (trifluoro methylsulfonyl) inferior amine salts of 1- methyl-1-propyl pyrrole alkane are configured to by ionic liquid, tetraethyl orthosilicate and first First mixed solution of acid composition, wherein weight percentage are as follows: tetraethyl orthosilicate 10%, 1- methyl-1-propyl pyrrole Bis- (trifluoro methylsulfonyl) inferior amine salts of alkane are 10%, formic acid 80%；Then, solid polyelectrolyte solution and first are mixed Solution is mixed according to mass ratio 1:1, is stirred evenly and is obtained composite solid electrolyte solution；
Second step, the composite solid electrolyte solution and positive electrode active materials LiFePO prepared using the first step4, conductive agent CNT and other additives (dispersing agent, if polyvinylpyrrolidone PVP) is according to preset mass ratio, specifically: composite solid electricity Electrolyte solution: LiFePO4: CNT: dispersing agent=10:85:4:1 ratio is compounded, and is homogenized, is coated with and drying atmosphere Middle drying, drying temperature are 60 DEG C, and drying time is 12 hours.It is dried in vacuum tank, drying temperature is 130 DEG C, drying time It is 24 hours.Prepare anode composite.
Third step, the composite solid electrolyte solution for reusing first step preparation is coated in compound collection, and is dried, Drying temperature is 60 DEG C, and drying time is 12 hours.Then, secondary drying is carried out in vacuum tank, drying temperature is 130 DEG C, Drying time is 24 hours, final to obtain the anode composite for having compounded composite solid electrolyte.
After acquisition has compounded the anode composite of composite solid electrolyte, by cooperating the metal aluminum foil table at 50 microns thick The battery cathode that the LiPON protective layer that bread covers 2 microns thick obtains can be assembled according to solid state lithium battery routine assembly method Solid state lithium battery.
Fig. 2 is the preparation method with the anode composite provided by the invention based on NEW TYPE OF COMPOSITE solid electrolyte, in reality The oxidizing potential test based on NEW TYPE OF COMPOSITE solid electrolyte and existing polyethylene glycol oxide PEO electrolyte for applying the preparation of example 1 is bent Line contrast schematic diagram, wherein A curve indicates that polyethylene glycol oxide PEO, B curve indicate composite solid electrolyte provided by the invention.
The NEW TYPE OF COMPOSITE solid electrolyte prepared in embodiment 1 is by solid polyelectrolyte, oxidation silicon substrate skeleton knot Structure compound and ionic liquid composition.Ionic liquid or oxidation silicon substrate gel structure are for being filled in solid polyelectrolyte master In body structure, may be implemented the lithium ion battery that solid electrolyte is prepared with active material and finally it is interelectrode it is soft contact, To reduce the interface impedance between active material, between the electrode and solid electrolyte of lithium ion battery, while improving electrolysis The anti-oxidant current potential of matter.Fig. 2 is that oxidizing potential test result is shown, with pure polyethylene glycol oxide PEO electrolyte phase ratio, the present invention The New Solid electrolyte of offer has higher oxidizing potential.
Embodiment 2
In specific embodiment 2, the present invention prepares the anode composite based on NEW TYPE OF COMPOSITE solid electrolyte, including following step It is rapid:
The first step, firstly, the lithium salts LiTFSI of the polymer P EO (400,000 molecular weight) of 5g, 5g is taken to be dissolved in the solvent four of 90g In hydrogen furans, be configured to solid polyelectrolyte solution, wherein weight percentage is: polymer P EO is 5%, lithium salts LiTFSI is 5%；Then, it takes 10g tetraethyl orthosilicate to be dissolved in 80g formic acid, and mixes 10g ionic liquid 1- methyl-1-the third Bis- (trifluoro methylsulfonyl) inferior amine salts of base pyrrolidines, it is molten to be configured to the mixing being made of ionic liquid, tetraethyl orthosilicate and formic acid Liquid, wherein weight percentage be: tetraethyl orthosilicate 10%, the ionic liquid 1- methyl-1-bis- (fluoroforms of propyl pyrrole alkane Sulphonyl) inferior amine salt be 10%；Finally, according to required composite solid electrolyte formula, by first step resulting polymers solid state electrolysis Tetraethyl orthosilicate/formic acid solution obtained by matter solution and second step, the mixing of 1:1 in mass ratio, stirs to obtain homogeneous mixture solotion.It stirs Mix to obtain mixed uniformly composite solid electrolyte solution.
Second step, the composite solid electrolyte solution and positive electrode active materials LiFePO prepared using the first step4, conductive agent CNT and other additives (dispersing agent, if polyvinylpyrrolidone PVP) is according to mass ratio, composite solid electrolyte solution: LiFePO4: CNT: dispersing agent=10:85:4:1 ratio is compounded, and is homogenized, is coated with and dry in dry atmosphere, is dried Dry temperature is 100 DEG C, and drying time is 12 hours, and secondary drying is then carried out in vacuum tank, and drying temperature is 100 DEG C, is dried The dry time is 24 hours, prepares anode composite.
At this time, can be used the first step preparation composite solid electrolyte solution and negative electrode active material (such as graphite), Conductive agent carbon black and other additives (dispersing agent, if polyvinylpyrrolidone PVP) is according to mass ratio, composite solid electrolyte: Graphite: carbon black: dispersing agent=10:85:4:1 ratio is compounded, and is homogenized, is coated with and dry in dry atmosphere, is dried Temperature is 100 DEG C, and drying time is 12 hours, and secondary drying is then carried out in vacuum tank, and drying temperature is 140 DEG C, drying Time is 24 hours, prepares composite negative pole.
Third step is respectively coated using composite solid electrolyte solution prepared by the first step in anode composite, composite negative pole On, and dry, drying temperature is 60 DEG C, and drying time is 12 hours, and secondary drying, drying temperature are then carried out in vacuum tank Be 130 DEG C, drying time be 24 hours, finally, can prepare the anode composite for having compounded composite solid electrolyte and The composite negative pole of composite solid electrolyte is compounded.
Finally, solid state lithium battery can be assembled according to solid state lithium battery routine assembly method.
Therefore, based on statement above it is found that compared with prior art, a kind of NEW TYPE OF COMPOSITE provided by the invention is positive And its preparation method and application battery, by effectively promoting the ionic conductivity that has of solid electrolyte, to guarantee solid State electrolyte is contacted with soft between electrode active material and solid electrolyte and battery electrode, reduces solid electrolyte and electrode Interface impedance between active material and solid electrolyte and battery electrode is conducive to widely production application, has great Production practices meaning.
By application NEW TYPE OF COMPOSITE anode provided by the invention, may be implemented using solid electrolyte and electrode active material And the electrolyte and combination electrode of solid electrolyte and interelectrode soft contact are battery component, so as to further prepare The solid state lithium battery of low impedance structure advantageously reduces the impedance of the solid state lithium battery finally prepared, is advantageously implemented solid-state lithium The large-scale application of battery.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of NEW TYPE OF COMPOSITE anode, which is characterized in that including composite solid electrolyte, positive electrode active materials, conductive agent and divide Powder, in which:
The weight percent that the composite solid electrolyte accounts for the anode composite is 1~30%；
The weight percent that the positive electrode active materials account for the anode composite is 50~98%；
The weight percent that the conductive agent accounts for the anode composite is 1~20%；
The weight percent that the dispersing agent accounts for the anode composite is 0~5%.
2. NEW TYPE OF COMPOSITE as described in claim 1 anode, which is characterized in that the composite solid electrolyte account for it is described it is compound just The weight percent of pole is 2~20%；
The weight percent that the positive electrode active materials account for the anode composite is 70~96%；
The weight percent that the conductive agent accounts for the anode composite is 2~10%；
The weight percent that the dispersing agent accounts for the anode composite is 0~3%；
The composite solid electrolyte includes the solid polyelectrolyte that weight percent is 10%~90%, 1%~60% Oxidation silicon substrate framework structured compound and 1%~60% ionic liquid.
3. NEW TYPE OF COMPOSITE anode as claimed in claim 2, which is characterized in that the solid polyelectrolyte includes weight hundred Divide than being 5%~50% lithium salts and 50%~95% polymer；
Cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, quaternary ammonium salt He in quaternary alkylphosphonium salt One kind, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluoro-phosphate radical [PF6]-, fluoroform Sulfimide root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-, nitrate anion [NO3]-, bromine Ion Br-With chloride ion Cl-One of；
The positive electrode active materials include cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material NCM, LiFePO4 LiFePO4, phosphorus Sour manganese lithium LiMnPO4With vanadium phosphate LiVPO4At least one of；
The conductive agent includes black carbon black, krypton cyanogen, active carbon, carbon nanotube CNT, graphene Graphene and graphite-like conductive agent At least one of；
The dispersing agent is polyvinylpyrrolidone PVP.
4. NEW TYPE OF COMPOSITE anode as claimed in claim 3, which is characterized in that the polymer includes polyethylene glycol oxide PEO, gathers At least one of acrylonitrile PAN, polyvinyl chloride PPC, polyethylene glycol oxide PEO modified structure and polyacrylonitrile (PAN) modified structure；
The lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4With six Fluorine arsenic acid lithium LiAsF6At least one of.
5. a kind of solid state lithium battery, which is characterized in that including NEW TYPE OF COMPOSITE anode as described in claim 1, composite solid electricity Solve matter layer and battery cathode；
The composite solid electrolyte layer is between the NEW TYPE OF COMPOSITE Anode and battery cathode.
6. a kind of preparation method of NEW TYPE OF COMPOSITE anode, which comprises the following steps:
Step 1: preparing composite solid electrolyte solution；
Step 2: by composite solid electrolyte solution, positive electrode active materials, conductive agent and dispersing agent, according to preset ratio into Row compounding mixing, and stir evenly, and be coated on plus plate current-collecting body, it then dries, prepares anode composite；
Step 3: composite solid electrolyte solution prepared by the first step, is coated on the anode composite again, then dries It is dry, it is final to obtain the anode composite for having compounded composite solid electrolyte.
7. preparation method as claimed in claim 6, which is characterized in that in second step, composite solid electrolyte, positive-active Mass ratio between material, conductive agent and dispersing agent is 5:85:8:2 or 10:85:4:1；
The positive electrode active materials include cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material NCM, LiFePO4 LiFePO4, phosphorus Sour manganese lithium LiMnPO4With vanadium phosphate LiVPO4At least one of；
The conductive agent includes black carbon black, krypton cyanogen, active carbon, carbon nanotube CNT, graphene Graphene and graphite-like conductive agent At least one of；
The dispersing agent is polyvinylpyrrolidone PVP.
8. preparation method as claimed in claim 6, which is characterized in that in second step, specific drying operation are as follows: be initially positioned at Dried in dry atmosphere, drying temperature is 40~130 DEG C, and drying time is 0~20 hour, be then placed on again in vacuum tank into Row secondary drying, drying temperature are 40~130 DEG C, and drying time is 0~60 hour.
9. preparation method as claimed in claim 6, which is characterized in that in the third step, composite solid electricity will be coated with first The anode composite of electrolyte solution is placed in dry atmosphere and dries, and drying temperature is 40~130 DEG C, and drying time is 0~20 small When, it is then placed in vacuum tank and is dried again, drying temperature is 40~130 DEG C, and drying time is 0~60 hour.
10. preparation method as claimed in claim 6, which is characterized in that the first step specifically includes the following steps:
Polymer and lithium salts are dissolved in preset solvent by the first sub-step, are configured to solid polyelectrolyte solution, wherein Polymer and lithium salts form solid polyelectrolyte together；
Second sub-step, tetraethyl orthosilicate is dissolved in formic acid, is then mixed with ionic liquid, is configured to by ionic liquid First mixed solution of body, tetraethyl orthosilicate and formic acid composition；
Third sub-step: it by solid polyelectrolyte solution and the first mixed solution, is mixed, is stirred according to preset quality ratio It mixes and uniformly obtains composite solid electrolyte solution；
In the first sub-step, the preset solvent is tetrahydrofuran；
In the first sub-step, the solid content of the solid polyelectrolyte solution is 1%~50%, and in composite solid In the solid content of electrolyte, the weight ratio between polymer and lithium salts is (1:1)~(95:5)；
The polymer includes polyethylene glycol oxide PEO, polyacrylonitrile (PAN), Kynoar PVDF, polyethylene glycol oxide PEO modification At least one of structure and polyacrylonitrile (PAN) modified structure；
The lithium salts includes bis trifluoromethyl sulfimide lithium LiTFSI, lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4With six Fluorine arsenic acid lithium LiAsF6At least one of；
In the second sub-step, in first mixed solution, the weight percent of ionic liquid is 1%~30%, former silicon The weight percent of sour tetra-ethyl ester is 1%~20%, and the weight percent of formic acid is 50%~98%；
Cation in the ionic liquid includes alkyl-substituted pyrroles, thiazole, piperidines, imidazoles, quaternary ammonium salt He in quaternary alkylphosphonium salt One kind, the anion in the ionic liquid includes tetrachloro aluminate [AlCl4]-, hexafluoro-phosphate radical [PF6]-, fluoroform Sulfimide root [(CF3SO2)2N]-, trifluoromethane sulfonic acid root [CF3SO3]-, tetrafluoroborate [BF4]-, nitrate anion [NO3]-, bromine Ion Br-With chloride ion Cl-One of；
In third sub-step, the preset mass ratio is 1:1.
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