CN108511708A - A kind of solid composite metal cathode of lithium - Google Patents

A kind of solid composite metal cathode of lithium Download PDF

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Publication number
CN108511708A
CN108511708A CN201810210158.XA CN201810210158A CN108511708A CN 108511708 A CN108511708 A CN 108511708A CN 201810210158 A CN201810210158 A CN 201810210158A CN 108511708 A CN108511708 A CN 108511708A
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lithium
solid
cathode
metal cathode
solid electrolyte
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张强
刘鹤
程新兵
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Tsinghua University
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Tsinghua University
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Priority to PCT/CN2018/094675 priority patent/WO2019174161A1/en
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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
    • 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
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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

A kind of solid composite metal cathode of lithium, the cathode are made of the composite layer and solid electrolyte protective layer two parts of lithium metal and close lithium framework material.Solid electrolyte protective layer includes inorganic solid electrolyte and organic solid-state electrolyte.Lithium metal is to fill by way of lithium, electrochemical deposition or physical mechanical mix to realize melting with the composite layer of close lithium framework material, and solid electrolyte protective layer is to be coated in compound layer surface by the methods of dipping, blade coating, spin coating, spraying or sputtering.The present invention can not only alleviate the volume expansion problem of cathode compared to common lithium piece cathode, and can regulate and control the depositing behavior of lithium metal, inhibit the growth of Li dendrite, improve the security performance and cycle life of lithium metal battery.In the test of lithium copper half-cell, which is 1~20%, is occurred without apparent dendrite in 20~5000 circle circulating batteries, and can improve the utilization rate of composite negative pole to 80~99.9999%.

Description

A kind of solid composite metal cathode of lithium
Technical field
The present invention relates to a kind of lithium anode, more particularly to a kind of solid composite metal cathode of lithium belongs to lithium metal electricity Pool technology field.
Background technology
The fast development of modern society makes requirement of the people to high-end energy storage device higher and higher, although traditional lithium from For sub- battery (especially graphite cathode) under continuous optimized development, practical energy density gradually levels off to theoretical boundary (372mAh g-1), but still be difficult to meet the requirement of many high specific energy energy storage devices, such as new-energy automobile (400Wh kg-1)。 Therefore, there is high theoretical capacity (3860mAh g-1) and most negative potential (- 3.040V vs. standard hydrogen electrodes) " Holy grail " gold Belong to cathode of lithium and obtains great concern.Using lithium metal as the lithium-sulfur cell of cathode and lithium-oxygen battery as the high ratio of a new generation Energy energy storage system, practical energy density are expected to reach 650Wh kg respectively-1With 950Wh kg-1, realize commercialized lithium at present The energy density of 2-3 times of ion battery meets the need of electric vehicle and portable, wearable electronic to energy density It asks.
Although lithium metal battery has many advantages and is widely applied foreground, it is suggested to from the 1970s Come that there are still some insoluble problems.The nonuniform deposition of lithium is easy to generate dendrite, the meeting of one side dendrite and electrolyte The reaction was continued causes the irreversible consumption of active lithium and electrolyte and the decline of battery coulombic efficiency, and another aspect dendrite is not Controllable growth is it is also possible to piercing through diaphragm, causing the short circuit of battery or even exploding, there are great security risks；In addition, and lithium Embedded graphite cathode in ion battery is compared, and the deposition of the lithium ion in lithium metal battery and deintercalation are no skeletal supports , this allows for dendrite and is easy to be detached from " dead lithium " that electrode surface formation can not be utilized again, while can also cause huge Volume expansion problem.In recent years, researcher propose numerous strategies solve the problems, such as lithium anode it is existing these：It is conductive The cathode framework material (graphene etc.) of close lithium can provide place for the deposition of lithium metal, and cathode is effectively relieved in cyclic process Volume expansion problem, while reducing the local current densities of lithium ion deposition/deintercalation, regulate and control forming core/deposition row of lithium ion For (the patent No.：CN105845891A)；Liquid state organic electrolyte is substituted with the solid electrolyte of high mechanical modulus, can not only be led to Cross the further growth that mechanical resistance inhibits Li dendrite, moreover it is possible to it is hidden to solve the inflammable and explosive safety brought of liquid state organic electrolyte Suffer from.
Although above two scheme can solve the problems, such as difference existing for lithium anode to a certain extent, golden The failure for belonging to lithium electrode is still unavoidable from, and there is presently no highly effective approach to solve each of lithium anode application simultaneously Kind problem.Therefore it is extremely urgent that a kind of combination kinds of schemes, the efficient strategy of complex protection lithium anode are designed.
Invention content
The object of the present invention is to provide a kind of solid composite metal cathode of lithium, by construct conductive close lithium cathode skeleton and It introduces solid electrolyte two methods and protects lithium anode jointly, work along both lines, inhibit lithium jointly from forming core and growth phase The growth of dendrite, alleviates the volume expansion problem of cathode, while improving the security performance of lithium metal battery.
Technical scheme is as follows：
A kind of solid composite metal cathode of lithium, it is characterised in that：The solid composite metal cathode of lithium is by lithium metal and parent The composite layer and solid electrolyte protective layer two parts of lithium framework material form；Solid electrolyte protective layer is multiple coated in skeleton Close the surface of layer.
In above-mentioned technical proposal, the composite layer of the lithium metal and close lithium framework material is to fill lithium, electrochemistry by melting Deposition or the mode of physical mechanical mixing are realized；The solid electrolyte protective layer be by dipping, blade coating, spin coating, spraying or Sputtering method is coated in the surface of skeleton composite layer.
Parent's lithium framework material of the present invention is preferably N doping, boron doping, bromine doping, gold particle modification, Argent grain The graphene of modification, carbon black, carbon nanotube, zinc oxide, silica, aluminium oxide modification foam copper and nickel foam in one kind or It is several.
Solid electrolyte protective layer of the present invention includes inorganic solid electrolyte and organic solid-state electrolyte, inorganic solid State electrolyte and the mass percent of organic solid-state electrolyte are respectively 0.1~40% and 60~99.9%.
Inorganic solid electrolyte of the present invention is preferably Li2+2xZn1-xGeO4、Li14Zn(GeO4)4、Na1+xZr2P3- xSixO12、Li1+xAlxTi2-x(PO4)3、Li1+xAlxGe2-x(PO4)、Li0.33La0.557TiO3、ABO3、D3E2(GO4)3、 Li5La3M2O12、Li7La3Zr2O12、Li6.75La3Zr1.75Ta0.25O12、Li10GeP2S12、xLi2S–(1-x)P2S5、75Li2S– (25-x)P2S5–xP2Se5、Li3PO4、Li3PS4、Li4SiO4、Li3N, LiF and Li2.9PO3.3N0.5In it is one or more, wherein A=Ca, Sr or La；B=Al or Ti；D=Ca, Mg, Y or La；E=Al, Fe, Ga, Ge, Mn, Ni or V；G=Si, Ge or Al；M =Nb or Ta；X is zero or positive number.
Organic solid-state electrolyte of the present invention is preferably lithium salts and the polyvinyl alcohol of diversion, polyethylene oxide, poly- Tetrafluoroethene, Polyurethane, polyacrylonitrile, polymethyl methacrylate, polyvinyl formal, gathers partially sodium carboxymethylcellulose Vinyl fluoride, Kynoar-hexafluoropropylene copolymer, perfluorinated sulfonic acid, polyvinyl butyral and one kind in polyvinyl chloride or Several mixtures, lithium salt are 0.01~20mol L-1。
Lithium salts of the present invention is lithium hexafluoro phosphate, hexafluoro lithium borate, hexafluoroarsenate lithium, lithium perchlorate, double ethanedioic acids It is one or more in lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine Huang imide lis and two (trimethyl fluoride sulfonyl) lithiums.
The present invention compared with prior art, has the following advantages that and high-lighting effect：The solid composite metal cathode of lithium Compared to common lithium piece cathode, parent's lithium framework material therein can alleviate volume expansion of the cathode in charge and discharge process and ask It inscribes, the close lithium site on skeleton can also regulate and control the forming core and depositing behavior of lithium metal, and Li dendrite is inhibited to generate；Solid electrolyte On the one hand the mechanical modulus that its can be utilized high hinders the further growth of Li dendrite, on the other hand can also solve liquid electrolyte The inflammable and explosive safety problem of liquid improves the security performance and cycle life of lithium metal battery.In lithium copper half-cell test system In, which is 1~20%, is followed in the battery of 20~5000 circles Occur without apparent dendrite in ring, and the utilization rate of the solid composite metal cathode of lithium can be improved to 80~99.9999%.
Specific implementation mode
A kind of solid composite metal cathode of lithium provided by the invention, the composition metal cathode of lithium include upper layer and lower layer, i.e. table The composite layer of face solid electrolyte protective layer and the lithium metal of bottom and close lithium framework material.
Lithium metal of the present invention and the compound of close lithium framework material are to fill lithium, electrochemical deposition or physics by melting The mode of mechanical mixture realizes that surface solid electrolyte protective layer can pass through the methods of dipping, blade coating, spin coating, spraying or sputtering Surface coated in lithium metal and close lithium framework material composite layer.
The close lithium framework material is N doping, boron doping, bromine doping, the graphite that gold particle is modified, Argent grain is modified One or more of alkene, carbon black, carbon nanotube, zinc oxide, silica, the foam copper of aluminium oxide modification and nickel foam.
The solid electrolyte protective layer includes inorganic solid electrolyte and organic solid-state electrolyte, ensures solid state electrolysis Matter has superpower hardness and toughness simultaneously, and inorganic solid electrolyte and the mass percent of organic solid-state electrolyte are respectively 0.1 ~40% and 60~99.9%.
The inorganic solid electrolyte is Li2+2xZn1-xGeO4、Li14Zn(GeO4)4、Na1+xZr2P3-xSixO12、Li1+ xAlxTi2-x(PO4)3、Li1+xAlxGe2-x(PO4)、Li0.33La0.557TiO3、ABO3、D3E2(GO4)3、Li5La3M2O12、 Li7La3Zr2O12、Li6.75La3Zr1.75Ta0.25O12、Li10GeP2S12、xLi2S–(1-x)P2S5、75Li2S–(25-x)P2S5– xP2Se5、Li3PO4、Li3PS4、Li4SiO4、Li3N, LiF and Li2.9PO3.3N0.5In it is one or more, wherein A=Ca, Sr or La；B=Al or Ti；D=Ca, Mg, Y or La；E=Al, Fe, Ga, Ge, Mn, Ni or V；G=Si, Ge or Al；M=Nb or Ta；x It is zero or positive number.
The organic solid-state electrolyte is the lithium salts and polyvinyl alcohol, polyethylene oxide, polytetrafluoroethylene (PTFE), carboxylic of diversion Sodium carboxymethylcellulose pyce, polyacrylonitrile, polymethyl methacrylate, polyvinyl formal, Kynoar, gathers partially at Polyurethane The mixing of one or more of viton copolymers, perfluorinated sulfonic acid, polyvinyl butyral and polyvinyl chloride Object, lithium salt are 0.01~20mol L-1。
The lithium salts be lithium hexafluoro phosphate, hexafluoro lithium borate, hexafluoroarsenate lithium, lithium perchlorate, biethyl diacid lithium borate, It is one or more in difluorine oxalic acid boracic acid lithium, double fluorine Huang imide lis and two (trimethyl fluoride sulfonyl) lithiums.
It is further appreciated that the present invention from following embodiment, but the present invention is not limited solely to following embodiment.
Embodiment 1：The method progress that lithium metal is filled with nitrogen-doped graphene by melting to lithium is compound, prepares nitrating graphite Alkene/lithium anode skeleton structure covers one layer of (0.01mol L containing lithium salts on cathode skeleton surface-1Lithium hexafluoro phosphate) it is poly- Vinyl alcohol (40%) and Li2ZnGeO4(60%) the Organic-inorganic composite solid electrolyte formed.The composition metal that will be prepared Cathode of lithium is applied in the test of lithium copper half-cell, and volume expansion of the cathode in charge and discharge process is 1%, and battery is enclosed 20 Occur without apparent dendrite in cycle, and the utilization rate of the composition metal cathode of lithium is up to 80%.
Embodiment 2：Lithium metal and the carbon nano-tube modified method progress that lithium is filled by melting of zinc oxide is compound, it prepares Zinc oxide is carbon nano-tube modified/lithium anode skeleton structure, cover one layer of (0.1mol L containing lithium salts on cathode skeleton surface-1 Lithium perchlorate) polyethylene oxide (25%) and Li5La3Nb2O12(75%) the Organic-inorganic composite solid electrolyte formed.It will The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, volume expansion of the cathode in charge and discharge process It is 5%, occurs without apparent dendrite in 5000 circle circulating batteries, and the utilization rate of the composition metal cathode of lithium is up to 90%.
Embodiment 3：Lithium metal and the hollow carbon balls that silica is modified are subjected to compound, system by the method for electrochemical deposition Hollow carbon balls/lithium anode skeleton structure is modified for silicon is gone out, one layer of (20mol L containing lithium salts is covered on cathode skeleton surface-1It is double Ethanedioic acid lithium borate) sodium carboxymethylcellulose (30%) and Li3PO4(70%) the Organic-inorganic composite solid state electrolysis formed Matter.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, body of the cathode in charge and discharge process Product is expanded to 10%, occurs without apparent dendrite in 2000 circle circulating batteries, and the utilization rate of the composition metal cathode of lithium is reachable 93%.
Embodiment 4：The method progress that lithium metal is filled with boron-doped graphite alkene by melting to lithium is compound, prepares boron-doped graphite Alkene/lithium anode skeleton structure covers one layer of (5mol L containing lithium salts on cathode skeleton surface-1Difluorine oxalic acid boracic acid lithium) it is poly- Tetrafluoroethene (35%) and Li0.33La0.557TiO3(65%) the Organic-inorganic composite solid electrolyte formed.By what is prepared Composition metal cathode of lithium is applied in the test of lithium copper half-cell, and volume expansion of the cathode in charge and discharge process is 20%, Occur without apparent dendrite in 1000 circle circulating batteries, and the utilization rate of the composition metal cathode of lithium is up to 95%.
Embodiment 5：Lithium metal is answered with the nickel foam that copper nano particles are modified by the method that mechanical-physical mixes It closes, prepares copper nano particles modifying foam nickel/lithium anode skeleton structure, covering one layer on cathode skeleton surface contains lithium salts (10mol L-1Hexafluoro lithium borate) Polyurethane (0.1%) and Li7La3Zr2O12(99.9%) Organic-inorganic composite formed is solid State electrolyte.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, the cathode is in charge and discharge process In volume expansion be 13%, occur without apparent dendrite in 5000 circle circulating batteries, and the utilization of the composition metal cathode of lithium Rate is up to 99.99%.
Embodiment 6：Lithium metal is subjected to compound, system with the foamy carbon that aluminium oxide is modified by the method that mechanical-physical mixes For aluminium oxide modifying foam nanocarbon/metal cathode of lithium skeleton structure is gone out, one layer of (15mol L containing lithium salts is covered on cathode skeleton surface-1 Double fluorine Huang imide lis) polyacrylonitrile (15%) and Na2Zr2P2SiO12(85%) the Organic-inorganic composite solid state electrolysis formed Matter.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, body of the cathode in charge and discharge process Product is expanded to 17%, occurs without apparent dendrite in the circulating battery of 300 circles, and the utilization rate of the composition metal cathode of lithium is reachable 88%.
Embodiment 7：The foam copper that lithium metal and silica are modified is carried out compound by the method that melting fills lithium, is prepared Silica modifying foam copper/lithium anode skeleton structure covers one layer of (18mol L containing lithium salts on cathode skeleton surface-1Two (trimethyl fluoride sulfonyl) lithium) polymethyl methacrylate (10%) and CaTiO3(90%) Organic-inorganic composite formed is solid State electrolyte.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, the cathode is in charge and discharge process In volume expansion be 3%, occur without apparent dendrite in the circulating battery of 600 circles, and the utilization of the composition metal cathode of lithium Rate is up to 99%.
Embodiment 8：By lithium metal with mix bromine graphene by melting fill lithium method carry out it is compound, prepare and mix bromine graphite Alkene/lithium anode skeleton structure covers one layer of (3mol L containing lithium salts on cathode skeleton surface-1Hexafluoroarsenate lithium) polyethylene Alcohol formal (5%) and Li6.75La3Zr1.75Ta0.25O12(95%) the Organic-inorganic composite solid electrolyte formed.It will prepare The composition metal cathode of lithium gone out is applied in the test of lithium copper half-cell, and volume expansion of the cathode in charge and discharge process is 12%, occur without apparent dendrite in the circulating battery of 800 circles, and the utilization rate of the composition metal cathode of lithium is up to 90%.
Embodiment 9：The carbon nanotube of lithium metal and gold nano particle modification is answered by the method for electrochemical deposition It closes, prepares gold nano particle modification carbon nanotube/lithium anode skeleton structure, covering one layer on cathode skeleton surface contains lithium Salt (4mol L-1Difluorine oxalic acid boracic acid lithium) Kynoar (1%) and 0.5Li2S–0.5P2S5(99%) organic-nothing formed Machine composite solid electrolyte.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, which is filling Volume expansion in discharge process is 8%, is occurred without apparent dendrite in the circulating battery of 3000 circles, and the composite metal lithium is negative The utilization rate of pole is up to 89%.
Embodiment 10：Lithium metal is subjected to compound, preparation with Zinc modified template carbon is aoxidized by the method that melting fills lithium Go out to aoxidize Zinc modified template nanocarbon/metal cathode of lithium skeleton structure, one layer of (6mol L containing lithium salts is covered on cathode skeleton surface-1It is double Ethanedioic acid lithium borate) Kynoar-hexafluoropropylene copolymer (12%) and Li2AlTi(PO4)3(88%) composition it is organic- Inorganic compounding solid electrolyte.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, which exists Volume expansion in charge and discharge process is 15%, is occurred without apparent dendrite in the circulating battery of 4000 circles, and the composition metal The utilization rate of cathode of lithium is up to 81%.
Embodiment 11：The method progress that lithium metal is filled with nitrogen doped carbon nanotube by melting to lithium is compound, prepares nitrating Carbon nanotube/lithium anode skeleton structure covers one layer of (8mol L containing lithium salts on cathode skeleton surface-1Lithium perchlorate) it is complete Fluosulfonic acid (18%) and Li2.9PO3.3N0.5(82%) the Organic-inorganic composite solid electrolyte formed.The compound gold that will be prepared Belong to cathode of lithium to be applied in the test of lithium copper half-cell, volume expansion of the cathode in charge and discharge process is 19%, in 700 circles Circulating battery in occur without apparent dendrite, and the utilization rate of the composition metal cathode of lithium is up to 96%.
Embodiment 12：The carbon nanotube of lithium metal and modified by silver nanoparticles is answered by the method for electrochemical deposition It closes, prepares modified by silver nanoparticles carbon nanotube/lithium anode skeleton structure, covering one layer on cathode skeleton surface contains lithium Salt (10mol L-1Lithium hexafluoro phosphate) polyvinyl butyral (23%) and Li14Zn(GeO4)4(77%) organic-nothing formed Machine composite solid electrolyte.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, which is filling Volume expansion in discharge process is 14%, is occurred without apparent dendrite in the circulating battery of 550 circles, and the composite metal lithium is negative The utilization rate of pole is up to 95%.
Embodiment 13：Lithium metal and the macropore carbon that silica is modified are subjected to compound, preparation by the method that melting fills lithium Go out silica modification macropore nanocarbon/metal cathode of lithium skeleton structure, one layer of (0.5molL containing lithium salts is covered on cathode skeleton surface-1Two (trimethyl fluoride sulfonyl) lithium) polyvinyl butyral (30%) and Li4SiO4(70%) the Organic-inorganic composite solid-state formed Electrolyte.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, the cathode is in charge and discharge process Volume expansion be 8%, occur without apparent dendrite in the circulating battery of 1200 circles, and the utilization rate of the composition metal cathode of lithium Up to 93%.
Embodiment 14：The method progress that lithium metal is mixed with the Zinc modified foam copper of oxidation by mechanical-physical is compound, Zinc oxide modifying foam copper/lithium anode skeleton structure is prepared, covering one layer on cathode skeleton surface contains lithium salts (2.5molL-1Biethyl diacid lithium borate) polyvinyl chloride (25%) and Li7La3Zr2O12(75%) organic and inorganic formed is multiple Close solid electrolyte.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, the cathode is in charge and discharge Volume expansion in the process is 16%, is occurred without apparent dendrite in the circulating battery of 1100 circles, and the composition metal cathode of lithium Utilization rate up to 92%.
Embodiment 15：Lithium metal and the template carbon that aluminium oxide is modified are subjected to compound, preparation by the method that melting fills lithium Go out aluminium oxide modification template nanocarbon/metal cathode of lithium skeleton structure, one layer of (3.5molL containing lithium salts is covered on cathode skeleton surface-1It is double Fluorine Huang imide li) polymethyl methacrylate (20%) and 75Li2S–20P2S5–5P2Se5(80%) organic-nothing formed Machine composite solid electrolyte.The composition metal cathode of lithium prepared is applied in the test of lithium copper half-cell, which is filling Volume expansion in discharge process is 6%, is occurred without apparent dendrite in the circulating battery of 900 circles, and the composite metal lithium is negative The utilization rate of pole is up to 94%.

Claims (7)

1. a kind of solid composite metal cathode of lithium, it is characterised in that：The solid composite metal cathode of lithium is by lithium metal and parent The composite layer and solid electrolyte protective layer two parts of lithium framework material form；The solid electrolyte protective layer is coated in institute State the surface of skeleton composite layer.
2. a kind of solid composite metal cathode of lithium described in accordance with the claim 1, it is characterised in that：The lithium metal and close lithium bone The composite layer of frame material is realized in such a way that melting fills lithium, electrochemical deposition or physical mechanical mixing；The solid state electrolysis Quality guarantee sheath is the surface that composite layer is coated in by dipping, blade coating, spin coating, spraying or sputtering method.
3. a kind of solid composite metal cathode of lithium described in accordance with the claim 1, it is characterised in that：The close lithium framework material Graphene, carbon black, carbon nanotube, zinc oxide, the oxygen modified for N doping, boron doping, bromine doping, gold particle modification, Argent grain One or more of SiClx, the foam copper of aluminium oxide modification and nickel foam.
4. according to a kind of solid composite metal cathode of lithium as claimed in claim 1,2 or 3, it is characterised in that：The solid-state electricity It solves quality guarantee sheath and includes inorganic solid electrolyte and organic solid-state electrolyte, inorganic solid electrolyte and organic solid-state electrolyte Mass percent is respectively 0.1~40% and 60~99.9%.
5. a kind of solid composite metal cathode of lithium according to claim 4, it is characterised in that：The inorganic solid-state electrolysis Matter is Li2+2xZn1-xGeO4、Li14Zn(GeO4)4、Na1+xZr2P3-xSixO12、Li1+xAlxTi2-x(PO4)3、Li1+xAlxGe2-x (PO4)、Li0.33La0.557TiO3、ABO3、D3E2(GO4)3、Li5La3M2O12、Li7La3Zr2O12、Li6.75La3Zr1.75Ta0.25O12、 Li10GeP2S12、xLi2S–(1-x)P2S5、75Li2S–(25-x)P2S5–xP2Se5、Li3PO4、Li3PS4、Li4SiO4、Li3N、LiF And Li2.9PO3.3N0.5In it is one or more, wherein A=Ca, Sr or La；B=Al or Ti；D=Ca, Mg, Y or La；E=Al, Fe, Ga, Ge, Mn, Ni or V；G=Si, Ge or Al；M=Nb or Ta；X is zero or positive number.
6. a kind of solid composite metal cathode of lithium according to claim 4, it is characterised in that：The organic solid-state electrolysis Matter is the lithium salts and polyvinyl alcohol, polyethylene oxide, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, Polyurethane, polypropylene of diversion Nitrile, polymethyl methacrylate, polyvinyl formal, Kynoar, Kynoar-hexafluoropropylene copolymer, perfluor The mixture of one or more of sulfonic acid, polyvinyl butyral and polyvinyl chloride, lithium salt are 0.01~20mol L-1。
7. a kind of solid composite metal cathode of lithium according to claim 6, it is characterised in that：The lithium salts is hexafluoro phosphorus Sour lithium, hexafluoro lithium borate, hexafluoroarsenate lithium, lithium perchlorate, biethyl diacid lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine Huang acyls are sub- It is one or more in amine lithium and two (trimethyl fluoride sulfonyl) lithiums.
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