CN109659474A - Rigid diaphragm and solid-state lithium metal battery - Google Patents

Rigid diaphragm and solid-state lithium metal battery Download PDF

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Publication number
CN109659474A
CN109659474A CN201710948057.8A CN201710948057A CN109659474A CN 109659474 A CN109659474 A CN 109659474A CN 201710948057 A CN201710948057 A CN 201710948057A CN 109659474 A CN109659474 A CN 109659474A
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China
Prior art keywords
rigid membrance
solid
lithium
rigid
coating
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CN201710948057.8A
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刘成勇
郭永胜
蔡挺威
范铨
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to CN201710948057.8A priority Critical patent/CN109659474A/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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

The application relates to the field of energy storage materials, in particular to a rigid membrane and a solid-state lithium metal battery. The rigid membrane is arranged between the solid electrolyte membrane and the anode plate of the solid-state lithium metal battery, and has certain hardness, so that extension or permeation of the lithium metal anode into the solid electrolyte membrane in the lithium metal battery assembling process can be inhibited, and the short circuit probability in the preparation process of the solid-state lithium metal battery can be reduced. The rigid membrane is made of at least one of metal elements and metal element-containing alloys, and can be alloyed with deposited lithium or contain the deposited lithium, so that the short circuit probability in the charge and discharge cycle process of the solid lithium metal battery can be reduced, and the cycle stability of the solid lithium metal battery can be improved.

Description

A kind of rigid membrance and solid-state lithium metal battery
Technical field
This application involves energy storage material fields, specifically, are related to a kind of rigid membrance and solid-state lithium metal battery.
Background technique
With the continuous improvement that people require energy density, conventional lithium ion battery has been difficult to meet increasing The demand of specific energy, then the metal lithium electrode with height ratio capacity inherent advantage becomes research hotspot.The specific capacity of lithium metal For 3860mAh/g, electrochemical potential is -3.04V (vs standard hydrogen electrode), lithium-sulfur cell, lithium-air battery etc. as anode The gravimetric energy density of lithium metal battery can achieve 400Wh/kg or more.
But lithium metal is used to as anode, it is also necessary to overcome the problems such as safety and cycle life, be mainly derived from The growth of Li dendrite may penetrate diaphragm, be easy to cause short circuit, cause security risk, seriously hinder high-capacity battery system Development and practical application.
In consideration of it, special propose the application.
Summary of the invention
The first aspect of the application proposes a kind of rigid membrance, which is characterized in that the rigid membrance is set to solid-state lithium Between the solid electrolyte diaphragm and anode of metal battery, the material of the rigid membrance is selected from metallic element, contains the gold Belong at least one of the alloy of element；The metallic element can form alloy with lithium.
The second aspect of the application proposes that a kind of solid-state lithium metal battery, the solid-state lithium metal battery include cathode pole Piece, solid electrolyte diaphragm and anode pole piece are provided with rigid film between the solid electrolyte diaphragm and the anode pole piece Piece.
The technical solution of the application at least has following beneficial effect:
The rigid membrance of the application is set between the solid electrolyte diaphragm of solid-state lithium metal battery and anode, due to rigid Property diaphragm use the material with certain degree of hardness to prepare, to can inhibit in lithium metal battery assembling process lithium anodes to solid Extension or infiltration in body electrolyte membrane, the short circuit probability in preparation process so as to reduce solid-state lithium metal battery.And And since rigid film can form alloy with the lithium deposition in solid state battery charging process or accommodate lithium deposition, can reduce Short circuit probability during the charge and discharge cycles of solid-state lithium metal battery, and the stable circulation of solid-state lithium metal battery can be improved Property.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the rigid membrance of a certain specific embodiment in the embodiment of the present application；
Fig. 2 is the structural schematic diagram of the rigid membrance of still another embodiment in the embodiment of the present application；
Fig. 3 is the structural schematic diagram of the rigid membrance of still another embodiment in the embodiment of the present application；
Fig. 4 is the structural schematic diagram of the solid-state lithium metal battery of a certain specific embodiment in the embodiment of the present application；
Fig. 5 is the structural schematic diagram of the solid-state lithium metal battery of still another embodiment in the embodiment of the present application；
Fig. 6 is all charging and discharging curves of head of the solid-state lithium metal battery of the embodiment of the present application 1.
Wherein:
1- cathode sheet；
11- cathode current collector；
12- cathode active material；
2- solid electrolyte diaphragm；
3- rigid membrance；
31- lithium ion conductor coating；
32- electronic conductor coating；
4- anode pole piece；
41- lithium metal or lithium alloy layer；
42- anode collector.
Specific embodiment
Combined with specific embodiments below, the application is further described.It should be understood that these embodiments are merely to illustrate the application Rather than limitation scope of the present application.
The embodiment of the present application proposes that a kind of rigid membrance, rigid membrance are set to the solid electrolyte of solid-state lithium metal battery Between diaphragm and anode, the material of rigid membrance is selected from least one of metallic element, the alloy containing the metallic element； Metallic element is the metallic element that alloy can be formed with lithium.
The rigid membrance of the embodiment of the present application is set between the solid electrolyte diaphragm of solid-state lithium metal battery and anode, In isolation cell assembling processes due to caused by natural compression lithium metal extend or infiltrate into dielectric film, to reach reduction Due to short-circuit risks, the raising solid-state lithium gold of cathode and lithium anodes contact and initiation in solid-state lithium metal battery assembling process Belong to the technical effect of circulating battery stability.
Metallic element used by the rigid membrance of the embodiment of the present application is selected from the metallic element that alloy can be formed with lithium, This is because, working as solid-state lithium metal battery during the charging process, deposit lithium metal and rigid membrance occur for lithium anodes surface Alloy is formed, rather than free lithium metal reduces short circuit so that the deposition that can inhibit lithium metal extends.In addition, working as solid state battery In electric discharge, contact of the solid electrolyte membrane with anode pole piece will lead in generation dissolution if it is the lithium metal of unhindered settling It is obvious to be deteriorated, influence subsequent charge and discharge process；And after the alloy lithium dissolution in the embodiment of the present application, the volume change of anode compared with It is small, stablize circulation conducive to solid state battery.
Further alternative, metallic element is selected from least one of Ge, Sn, Al, Ga, In, Mg, Zn.
Further alternative, the material of rigid membrance is further selected from the alloy that above-mentioned metallic element and lithium are formed.
Optionally, rigid membrance with a thickness of 1 μm~1000 μm, the upper limit of the thickness of rigid membrance can be 1000 μm, 950 μm、900μm、850μm、800μm、750μm、700μm、650μm、600μm、550μm、500μm、450μm、400μm、450μm、 400μm、350μm、300μm、250μm、200μm、150μm、100μm、90μm、80μm、70μm、60μm、50μm、40μm、30μm、 20 μm, 15 μm, 10 μm, the lower limit of the thickness of rigid membrance can for 1 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5μm,6μm,6.5μm,7.5μm,8μm,8.5μm,9μm,9.5μm.The range of the thickness of rigid membrance can have upper and lower bound Any number composition.If the thickness of rigid membrance is too low, rigid membrance is frangible, easy wrinkle, cannot function well as suppression The effect that lithium metal processed extends, if rigid membrance is blocked up, and will affect the energy density of battery.The thickness of rigid membrance is preferred It is 3 μm~1000 μm, more preferably 5 μm~50 μm.
Optionally, the elasticity modulus of rigid membrance is greater than or equal to 5GPa.Further, the elasticity modulus of rigid membrance Range is 5GPa~100GPa.If the elasticity modulus of rigid membrance is too low, solid-state lithium metal battery cannot be stopped well The extension and infiltration of lithium metal in preparation process.
As a kind of improvement of the application rigid membrance, at least one surface of rigid membrance is provided with coating, coating Material is selected from lithium ion conductor, electronic conductor or electronics-lithium ion mixed conductor, to further increase the lithium ion of rigid membrance Conductive performance or electronic conductivity energy.
Further alternative, coating may be disposed on a surface of rigid membrance, may also set up opposite in rigid membrance Two surfaces on.
It is further alternative, coating with a thickness of 10nm~200 μm.The upper limit of coating layer thickness can for 200 μm, 180 μm, 150μm、120μm、100μm、75μm、50μm、25μm、20μm、15μm、10μm、5μm、3μm、2μm、1μm、900nm、800nm、 700nm, 600nm, 500nm, 400nm, 300nm, 250nm, 200nm, the lower limit of the thickness of coating can for 10nm, 20nm, 30nm, 40nm, 50nm, 70nm, 90nm, 100nm, 120nm, 150nm, 180nm, 190nm, the range of the thickness of coating can have the upper limit and Any number of lower limit forms.If cover light, the effect for improving battery conductive or leading lithium ion cannot be functioned well as； If overweight coating, the lithium ion or electron-transport impedance that will lead in anode active material layer increase, and battery polarizes.
As a kind of example of the application rigid membrance, the only one surface of rigid membrance is provided with lithium ion conductor painting Layer, for structural schematic diagram as shown in Figure 1, in Fig. 1, a surface of rigid membrance 3 is provided with lithium ion conductor coating 31.
As a kind of example of the application rigid membrance, the only one surface of rigid membrance is provided with electronic conductor coating； For its structural schematic diagram as shown in Fig. 2, in Fig. 2, a surface of rigid membrance 3 is provided with electronic conductor coating 32.
As a kind of example of the application rigid membrance, a surface of rigid membrance be provided with lithium ion conductor coating, Another surface is provided with electronic conductor coating.Its structural schematic diagram is as shown in figure 3, in Fig. 3, a table of rigid membrance 3 Face is provided with lithium ion conductor coating 31, another surface is provided with electronic conductor coating 32.
It is further alternative, lithium ion conductor coating with a thickness of 50nm~200 μm, preferably 500nm~100 μm.
It is further alternative, electronic conductor coating with a thickness of 10nm~200 μm, preferably 50nm~50 μm.
The preparation method of the embodiment of the present application coating have no it is specifically limited, using method known to those skilled in the art , such as spin coating, spraying or deposition etc..
Further alternative, lithium ion conductor is selected from can embedding oxidate for lithium, simple substance coating, copolymer solid electrolyte, sulphur At least one of compound solid electrolyte, solid oxide electrolyte.
Wherein, can embedding oxidate for lithium be selected from SiO, Fe2O3、CuO、TiO2、MnO2、SnO、SnO2At least one of.
Wherein, the material of simple substance coating is selected from least one of Al, In, Mg, Sn, Ge, Si, C, Pb, Sb, Bi.
Wherein, copolymer solid electrolyte includes polymer body and lithium salts, polymer body be selected from polyether-based polymers, At least one of polyolefin polymers, polynitriles quasi polymer, polycarboxylate quasi polymer, lithium salts are 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；
Further, in copolymer solid electrolyte, the mass ratio of polymer body and lithium salts be 20~80:80~ 20；
Further, in copolymer solid electrolyte, polyether-based polymers are selected from polyethylene oxide (PEO), polycyclic oxygen At least one of propane (PPO), polyethylene glycol (PEG), polyethylene glycol dimethyl ether (PEGDME), polysiloxanes；
Polyolefin polymers are selected from polyethylene (PE), polypropylene (PP), gather inclined tetrafluoroethene (PVDF), polyvinylidene fluoride At least one of alkene-hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE) (PTFE), polyvinyl chloride (PVC)；
Polynitriles quasi polymer is selected from least one of polyacrylonitrile (PAN), poly- Melamine；
Polycarboxylate quasi polymer be selected from polymethyl methacrylate (PMMA), in polymethyl acrylate (PMA) at least It is a kind of；
Polycarbonate polymer is selected from least one of polypropylene carbonate (PC), poly- ethylenecarbonate (PEC).
Further, in copolymer solid electrolyte, the fast lithium ion conductor of oxide, which is selected from, has NASICON (Na+ Super ionic conductor) structure compound, have LISICON (Li+Super ionic conductor) structure Compound, the compound with garnet (Garnet) structure, with perovskite (Pervoskite) structure compound in At least one.Wherein, the compound with NASICON structure can be selected from LiM2(PO4)3, M is selected from Ti, Zr or Ge；Have The compound of LISICON structure can be selected from Li14Zn(GeO4)4；Compound with garnet structure can be selected from Li7La3M2O12, M Selected from transition metal, more preferable Zr or Sn；Compound with perovskite structure can be selected from Li3xLa1-3xTiO3, 0 < x < 0.16.
Further, in copolymer solid electrolyte, the fast lithium ion conductor of sulfide is selected from yLi2S-(100-y)P2S5 With MS2Or the mixture of LiqQ, wherein 1 < y < 100, M are selected from Si, Ge, Sn, and Q is selected from F, Cl, Br, I, O, N, PO4 3-、SO4 2-、 BO3 3-、SiO4 4-、PF6 -、(FSO2)N-、(CF3SO2)N-, q be 1~4 integer.Wherein, the form of the fast lithium ion conductor of sulfide It can be one of glassy state, crystalline state or glass-crystal mixed state.
Wherein, sulfide solid electrolyte is selected from yLi2S-(100-y)P2S5With MS2Or the mixed system of LiqQ, wherein 1 < y < 100, M are selected from Si, Ge, Sn, and Q is selected from F, Cl, Br, I, O, N, PO4 3-、SO4 2-、BO3 3-、SiO4 4-、(FSO2)N-、(CF3SO2) N-, q be 1~4 natural number；The form of sulfide electrolyte can be one in glassy state, crystalline state or glass-crystal mixed state Kind.
Wherein, solid oxide electrolyte, which is selected from, has NASICON (Na+Super ionic conductor) structure Compound has LISICON (Li+Super ionic conductor) structure compound, have garnet (Garnet) knot At least one of the compound of structure, compound with perovskite (Pervoskite) structure.Wherein, there is NASICON knot The compound of structure can be selected from LiM2(PO4)3, M is selected from Ti, Zr or Ge；Compound with LISICON structure can be selected from Li14Zn (GeO4)4；Compound with garnet structure can be selected from Li7La3M2O12, M is selected from transition metal, more preferable Zr or Sn；Have The compound of perovskite structure can be selected from Li3xLa1-3xTiO3, 0 < x < 0.16.
Further, when coating is lithium ion conductor coating, lithium ion conductor coating with a thickness of 50nm~200 μm, Preferably 500nm~100 μm.
The one side that lithium ion conductor coating is provided in solid-state lithium metal battery, on rigid membrance can be towards anode pole Piece, can also be towards solid electrolyte diaphragm, and more preferably towards solid electrolyte diaphragm.
Wherein, electronic conductor is selected from conductive black (super-P), acetylene black, vapor-grown carbon fibers (Vapor-grown Carbon fiber, abbreviation VGCF), carbon nanotube, graphite, hard carbon, soft carbon, carbonaceous mesophase spherules (abbreviation MCMB), graphene At least one of.
Further, when coating be electronic conductor when, coating with a thickness of 10nm~200 μm, preferably 50nm~50 μm.
The one of electronic conductor coating is provided in solid-state lithium metal battery, on rigid membrance facing towards anode pole piece.
The second aspect of the embodiment of the present application proposes that a kind of solid-state lithium metal battery, solid-state lithium metal battery include cathode pole Piece, solid electrolyte diaphragm and anode pole piece, are provided with rigid membrance between solid electrolyte diaphragm and anode.Solid-state lithium metal Battery is laminated battery plate.
Illustratively, the structural schematic diagram of solid-state lithium metal battery is as shown in figure 4, in Fig. 4, solid-state lithium metal battery packet Include anode pole piece 4, solid electrolyte diaphragm 2, rigid membrance 3 and cathode sheet 1.Wherein, cathode sheet 1 includes cathode active material The bed of material 12 and cathode current collector 11, anode pole piece 4 include lithium metal or lithium alloy layer 41 and anode collector 42.
Illustratively, the structural schematic diagram of solid-state lithium metal battery is as shown in figure 5, in Fig. 5, solid-state lithium metal battery packet Include anode pole piece 4, solid electrolyte diaphragm 2, rigid membrance 3 and cathode sheet 1.Wherein, cathode sheet 1 includes cathode active material The bed of material 12 and cathode current collector 11, anode pole piece 4 include lithium metal or lithium alloy layer 41 and anode collector 42；Rigid membrance 3 A surface be provided with lithium ion conductor coating 31, another surface is provided with electronic conductor coating 32.
The cathode sheet of the embodiment of the present application, solid electrolyte diaphragm and anode pole piece are illustrated respectively below.
[cathode sheet]
Cathode sheet includes cathode current collector and cathode active material layer, in cathode active material layer comprising cathode material, Solid electrolyte, conductive additive and binder, cathode current collector can be selected from aluminium foil, utter misery aluminium foil, at least one in stainless steel Kind.
It is further alternative, active material of cathode, solid electrolyte, conductive agent, binder mass ratio be 48~90:8 ~50:1~10:1~10, preferably 60~75:15~30:5:5.In cathode sheet, each component content influences whether cathode pole In piece electronics and lithium ion conducting network building, if active material of cathode ratio be higher than 90%, will lead to solid electrolyte, The content of conductive additive and binder is too low, is unfavorable for the transmitting of electronics and lithium ion；If active material of cathode ratio is low In 48%, the capacity of battery can be reduced, battery energy density is influenced.
It is further alternative, cathode active material layer with a thickness of 10~200 μm.If cathode active material layer is excessively thin, Then battery energy density is caused to reduce；If cathode active material layer is blocked up, will increase lithium in cathode active material layer from Sub- transfer impedance, battery polarize.
Further alternative, active material of cathode is selected from the olivine structural lithium metal oxidation that can deviate from, receive lithium ion In object, layer structure lithium metal oxide, spinel structure lithium metal oxide and material after being modified to the above material At least one.
Wherein, olivine structural lithium metal oxide is selected from such as LiFePO4 (LiFePO4), cobalt phosphate lithium (LiCoPO4)、 Lithium manganese phosphate (LiMnPO4), LiNiPO (LiNiPO4), ferric phosphate (FePO4At least one of)；
Layer structure lithium metal oxide can be selected from such as cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), ternary material LiNisBtC(1-s-t)O2(wherein, B, C be independently selected from least one of Co, Al, Mn, and B and C be not identical, and 0 < s < 1,0 < t < At least one of 1))；
Spinel structure lithium metal oxide can be selected from LiMn2O4 (LiMn2O4), nickel ion doped (LiNi0.5Mn1.5O4)。
Modified material can be selected from adulterating above-mentioned material and coat treated material, further, doping and cladding Element can be selected from metallic element and nonmetalloid, as Li, N, F, Cl, S, B, P, Al, Si, Zr, Ti, Ge, Sn, Mg, Zn, Ce, W, V etc..And one or more of mixtures of above-mentioned substance.
Further alternative, solid electrolyte can be selected from sulfide solid electrolyte.
Specifically, sulfide solid electrolyte is selected from yLi2S-(100-y)P2S5With MS2Or the mixed system of LiqQ, In, 1 < y < 100, M are selected from Si, Ge, Sn, and Q is selected from F, Cl, Br, I, O, N, PO4 3-、SO4 2-、BO3 3-、SiO4 4-、(FSO2)N-、 (CF3SO2)N-, q be 1~4 natural number.The form of sulfide electrolyte can be glassy state, crystalline state or glass-crystal mixed state One of.
In cathode active material layer, binder is selected from PVDF, PTFE, PAALi, butadiene-styrene rubber, nitrile rubber, butylene rubber At least one of glue, styrene rubber or polyurethane.
In cathode active material layer, conductive additive is selected from conductive black (super-P), acetylene black, vapor-grown carbon At least one of fiber (Vapor-grown carbon fiber, abbreviation VGCF), carbon nanotube.
The embodiment of the present application cathode sheet can be used following methods and be prepared, specifically includes the following steps:
In protective gas atmosphere, by active material of cathode, solid electrolyte, conductive agent, binder with certain mass ratio After mixing, suitable organic solvent is added and is mixed and made into slurry, is coated on cathode current collector surface, is compacted after dry, yin is made Pole pole piece.The dosage of organic solvent is regulated and controled according to the viscosity of slurry, and the viscosity for controlling slurry is 5000~200000mPa S, preferably 10000~50000mPas.Slurry viscosity is excessive, increases pole piece manufacture difficulty, and viscosity is too low, is easy to cause list The upper activity substance content of plane product reduces, and reduces the energy density of battery.
In the preparation process of cathode sheet, it is organic that organic solvent is selected from ether organic solvent, hydrocarbon organic solvent, esters At least one of solvent, nitrile organic solvent, amide-type organic solvent, alcohol organic solvent, halogenated organic solvent.
Specifically, ether organic solvent is selected from least one of ether, tetrahydrofuran, glycol dimethyl ether, hydro carbons has Solvent is selected from least one of pentane, n-hexane, hexamethylene, toluene, dimethylbenzene, trimethylbenzene, based organic solvent choosing From at least one of ethyl acetate, methyl formate, repefral, nitrile organic solvent is selected from acetonitrile, amides Organic solvent is selected from N-Methyl pyrrolidone (NMP) and/or n,N-Dimethylformamide (DMF), and alcohol organic solvent is selected from second Alcohol；Halogenated organic solvent is selected from methylene chloride and/or 1,2- dichloroethanes.
Further alternative, protective gas is nitrogen or inert gas, the preferred argon gas of inert gas.
Further alternative, compaction pressure is 20MPa~500MPa, preferably 200MPa~300MPa, and compacted density is 1.8g/cm3~4.2g/cm3, compacting temperature is 25 DEG C~150 DEG C.
Further alternative, hybrid mode can be using row mixing method known in the industry, such as magnetic agitation, mechanical ball mill Deng not requiring excessively.
[solid electrolyte diaphragm]
Solid electrolyte diaphragm includes solid electrolyte and binder.Wherein, electrolyte, binder mass ratio can be 99~50:1~50, preferably 98~80:2~20.In the composition of solid electrolyte diaphragm, if the content mistake of binder It is low, it will lead to electrolyte film strength and poor toughness；If the too high levels of binder, the transmitting of lithium ion will affect, electricity It polarizes in pond.
Further, solid electrolyte diaphragm with a thickness of 10~500 μm.If solid electrolyte diaphragm is excessively thin, electricity Solution matter is frangible, and short circuit easily occurs for battery；If solid electrolyte diaphragm is blocked up, the energy density of battery can be reduced.
Further, solid electrolyte is sulfide solid electrolyte, and sulfide solid electrolyte can be 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-、(FSO2)N-、(CF3SO2)N-, q be 1~4 natural number.The form of sulfide electrolyte can For one of glassy state, crystalline state or glass-crystal mixed state.
Wherein, binder is selected from PVDF, PTFE, PAALi, PVDF-HFP, butadiene-styrene rubber, nitrile rubber, butene rubber, benzene At least one of ethylene rubber or polyurethane.
The embodiment of the present application solid electrolyte diaphragm can be used following methods and be prepared, specifically includes the following steps:
The mixed dissolution into organic solvent is added in binder in glove box (oxygen content < 1ppm, water content < 1ppm) Afterwards, it adds in sulfide electrolyte, the slurry prepared after continueing to mix 1 hour；The slurry is spread evenly across glass On glass substrate, after naturally dry 1~3 hour, after vacuum high-temperature is 1~3 hour dry, it will be made after the compacting of sulfide electrolyte membrane At diaphragm.
Wherein, the dosage of organic solvent is regulated and controled according to electrode slurry viscosity, control slurry viscosity be 5000~ 200000mPas, preferably 10000~50000mPas.If slurry viscosity is excessive, it is difficult that dielectric film production can be increased Degree, viscosity is too low, then easily leads to dielectric film and hole occur, increases the risk of battery internal short-circuit to a certain extent.
[anode pole piece]
Anode pole piece includes lithium metal or lithium alloy layer and anode collector, and anode collector is selected from copper foil, utter misery copper At least one of foil, stainless steel foil.
The embodiment of the present application anode pole piece can be used following methods and be prepared, specifically includes the following steps: by lithium metal Or lithium alloy is affixed on anode collector surface.
Wherein, lithium metal or lithium alloy layer with a thickness of 1 μm~200 μm, preferably 5 μm~100 μm.
Following methods preparation can be used in solid-state lithium metal battery in the embodiment of the present application, specifically includes step:
1, prepare cathode sheet: by active material of cathode, solid electrolyte, conductive agent, binder with it is suitable organic molten Agent is mixed and made into slurry, is coated on cathode current collector surface, is compacted after dry.
2, it prepares solid electrolyte diaphragm: sulphur will be configured in solid electrolyte, binder and appropriate organic solvent solution This sulfide electrolyte slurry is coated on glass baseplate by compound electrolyte slurry, is compacted after dry.
3, it prepares anode pole piece: lithium metal or lithium alloy being affixed on anode collector surface, anode pole piece is made.
4, rigid membrance is prepared: by Lithium Ionic Conducting Materials or electron conductor material or lithium ion-electronic conductor composite wood Expect, at least one surface coated on rigid membrance, or does not apply, rigid membrance is made.
5: preparation solid-state lithium metal battery: cathode sheet, solid electrolyte diaphragm, anode pole piece, rigid membrance being distinguished It is sliced by required size, cathode sheet, solid electrolyte diaphragm, anode pole piece, the rigid membrance after slice is pressed into center Alignment stacks gradually into sandwich layer unit, and sandwich layer unit is pressurizeed at a certain temperature and is combined with each other, and forms solid-state lithium gold Belong to battery battery core.
Wherein, compaction pressure when pressurization is 20MPa~500MPa, preferably 200MPa~300MPa；Compacting temperature Range is 25 DEG C~150 DEG C.
Embodiment
Embodiment 1
1, prepared by cathode sheet: in glove box, by active material LiCoO2, sulfide solid electrolyte Li3PS4, conductive agent VGCF, binder butadiene-styrene rubber (number-average molecular weight is about 500,000) are mixed in THF solvent, sufficiently by weight 70:20:5:5 After being uniformly mixed, it is coated on aluminium foil surface, is dried after naturally dry through 60 DEG C, cold pressing, slice, obtains LiCoO2Cathode is living Property material layer, cathode active material layer with a thickness of 50 μm.
2, prepared by solid electrolyte membrane: in glove box, by sulfide electrolyte Li3PS4With binder butadiene-styrene rubber by weight Amount is mixed in THF solvent than 99:1 and is configured to electrolyte slurry, be applied to glass surface, and dry at 60 DEG C, is electrolysed Plasma membrane is obtained after being sliced with a thickness of 50 μm of solid electrolyte diaphragms.
3, prepared by rigid membrance: will be sliced with a thickness of 8 μm, the aluminium foil that elasticity modulus is 10GPa.
4, prepared by anode pole piece: 25 μm of lithium metal layers being affixed on copper foil surface, are sliced.
5, prepared by solid-state lithium metal battery: above-mentioned cathode sheets, solid electrolyte membrane, rigid membrance, anode pole piece are pressed Sequence center is aligned lamination, and 2min is cold-pressed at room temperature, 250MPa and obtains battery core unit, and 10 layers of battery core unit cold pressing are placed on It is encapsulated in outer packing, solid-state lithium metal battery is obtained after forming.
Embodiment 2
Essentially identical with the preparation method of embodiment 1, difference is: in rigid membrance preparation process, the thickness of aluminium foil 3 μm are replaced with by 8 μm.
Embodiment 3
Essentially identical with the preparation method of embodiment 1, difference is: in rigid membrance preparation process, the thickness of aluminium foil 1000 μm are replaced with by 8 μm.
Embodiment 4
Essentially identical with the preparation method of embodiment 1, difference is: in cathode sheet preparation process, active material by LiCoO2Replace with LiFePO4, solid electrolyte is by Li3PS4Replace with Li7P3S11。
In solid electrolyte membrane preparation process, solid electrolyte is by Li3PS4Replace with Li7P3S11。
In rigid membrance preparation process, material replaces with indium foil by aluminium foil, indium foil with a thickness of 8 μm, elasticity modulus is 4GPa。
Embodiment 5
Essentially identical with the preparation method of embodiment 4, difference is:
In rigid membrance preparation process, material, which replaces with group by aluminium foil, becomes the poly- of LiTFSI-PEO (80:20, weight ratio) Polymer electrolyte membrane, polymer dielectric film with a thickness of 25 μm, elasticity modulus 1GPa.
Embodiment 6
Essentially identical with the preparation method of embodiment 1, difference is:
In cathode sheet preparation process, active material is by LiCoO2Replace with LiNi0.6Co0.2Mn0.2O2, solid electrolyte by Li3PS4Replace with Li6PS5Cl。
In solid electrolyte membrane preparation process, solid electrolyte is by Li3PS4Replace with Li6PS5Cl。
Lithium ion conductor coating is coated on one surface of rigid membrance, the preparation method comprises the following steps: in aluminium foil surface spin coating The group of 50nm thickness becomes the polymer dielectric coating of LiTFSI-PEO (80:20, weight ratio).Laminated batteries preparation process In, coated side containing lithium ion conductor is close to solid electrolyte diaphragm.
Embodiment 7
Essentially identical with the preparation method of embodiment 6, difference is: rigid aluminium foil surface coats lithium ion conductor coating Group become SiO, with a thickness of 5 μm.
Embodiment 8
Essentially identical with the preparation method of embodiment 6, difference is: rigid aluminium foil surface coats lithium ion conductor coating Group become In, with a thickness of 200 μm.
Embodiment 9
Essentially identical with the preparation method of embodiment 6, difference is: rigid aluminium foil surface coats lithium ion conductor coating Group become graphite, with a thickness of 5 μm.
Embodiment 10
Essentially identical with the preparation method of embodiment 1, difference is in cathode sheet preparation process, active material by LiCoO2Replace with LiNi0.8Co0.1Mn0.1O2, solid electrolyte is by Li3PS4Replace with Li6PS5Cl。
In solid electrolyte membrane preparation process, solid electrolyte is by Li3PS4Replace with Li10GeP2S12(LGPS)。
Rigid membrance surface coats electronic conductor coating, preparation process are as follows: is being 10GPa's with a thickness of 8 μm, elasticity modulus The amorphous carbon of aluminium foil surface coating 10nm thickness.In laminated batteries preparation process, coated side containing electronic conductor is close to anode pole Piece.
In anode pole piece preparation process, anode replaces with Li-In alloy by lithium metal, with a thickness of 25 μm.
Embodiment 11
Essentially identical with the preparation method of embodiment 10, difference is: the group of aluminium foil surface coating electronic conductor coating As graphite, with a thickness of 5 μm.
Embodiment 12
Essentially identical with the preparation method of embodiment 10, difference is: the group of aluminium foil surface coating electronic conductor coating As graphene, with a thickness of 200 μm.
Embodiment 13
Essentially identical with the preparation method of embodiment 1, difference is: coating lithium ion conductor in the one side of aluminium foil and applies The group of layer, lithium ion conductor coating becomes Li3PS4, with a thickness of 5 μm.Electronic conductor coating is coated on aluminium foil surface another side, The group of electronic conductor coating becomes graphene, with a thickness of 5 μm.In laminated batteries preparation process, coated side containing lithium ion conductor is leaned on Nearly solid electrolyte diaphragm, coated side containing electronic conductor is close to anode pole piece.
Comparative example 1
Essentially identical with the preparation method of embodiment 1, difference is: being free of rigid membrance.
Comparative example 2
Essentially identical with the preparation method of embodiment 1, difference is: being Li-In alloy in anode pole piece.
Comparative example 3
Essentially identical with the preparation method of embodiment 1, difference is: metallic lithium layer is free of in anode pole piece.
Comparative example 4
Essentially identical with the preparation method of comparative example 3, difference is: rigid membrance surface coats electronic conductor coating, The group of electronic conductor coating becomes graphite, with a thickness of 5 μm.
The design parameter of embodiment 1~13 and comparative example 1~4 is as shown in table 1.
Table 1
Wherein, "/" indicates the not set structure.
Test method:
Battery testing: charge/discharge operation voltage range be set as 2.8V~4.2V (Examples 1 to 3,6~13, comparative example 1 ~4) loop test and 2.8V~4.0V (embodiment 4 and 5), is carried out by the way of constant current charge-discharge, wherein test electric current is (current density is about 0.13mA/cm to 0.1C2), test temperature is 30 DEG C.Experimental result is as shown in table 2.
1, first all specific capacities
Under 0.1C charging and discharging currents, all specific discharge capacities of head of battery are tested.Experimental result is as shown in table 2.
2, first all coulombic efficiencies
Under 0.1C charging and discharging currents, all coulombic efficiencies of head of battery are tested；Experimental result is as shown in table 2.
All charge specific capacity × 100% of all specific discharge capacity/head of all coulombic efficiency=head of the head of battery.
3, energy density
The energy density of battery is tested, experimental result is as shown in table 2.
All specific capacity × cathode active material quality × mean voltage/battery the gross masses of the energy density of battery=head.
4, loop test
After battery to be recycled to 50 weeks and 200 weeks respectively, the capacity retention ratio of battery is tested respectively.Experimental result such as 2 institute of table Show.
Capacity retention ratio=50 week or all specific discharge capacity × 100% of 200 weeks specific discharge capacities/head.
5, in the preparation process of 100 pieces of solid-state lithium metal batteries of statistics preparation, the quantity of the battery of short circuit, statistics hair occurs The ratio of the battery of raw short circuit.Experimental result is also as shown in table 2.
Table 2
Wherein, "/" indicates that surveyed battery is short-circuit.
Compared with comparative example 1 it is found that embodiment 1~13, comparative example 3~4 by using rigid membrance after can obviously press down The short circuit phenomenon of solid-state lithium metal battery processed, all charging and discharging curves of the head of 1 battery of embodiment are as shown in Figure 6.
Comparing embodiment 1~3 is it is found that the thickness of rigid membrance Al foil is affected to battery performance, (3 μ when Al foil is relatively thin M), short circuit (embodiment 2, circulation short circuit after 83 weeks) cannot effectively be inhibited, but when Al foil is too thick (100 μm), alloy reaction can be led Cause the decaying in battery charge and discharge process too fast and energy density reduction.
Comparing embodiment 1,4,5 and comparative example 1~2 it is found that the type and elasticity modulus of rigid membrance to the performance of battery Influence is more obvious, wherein rigid high material can obviously inhibit short-circuit (such as Al foil, embodiment 1), it is short when the rigidity of film reduces Road probability is higher (such as thin polymer film, embodiment 5).
Comparing embodiment 1 and comparative example 3~4 are it is found that since the lithium metal of Al and deposition will form the alloy of low electric conductivity LiAl causes cell decay to be accelerated, therefore has lithium metal to show higher cyclical stability as the embodiment 1 of lithium source.This Outside, in comparative example 4, after the surface Al coats graphite, the electron conduction of system is increased, specific capacity is played also above comparative example 3.
Comparing embodiment 1 and embodiment 6~9 affect cyclic process it is found that after the surface Al coating lithium ion conductive material The lithium ion conduction electric conductivity of middle galvanic anode side.Wherein, the material (embodiment 7~9) of high-lithium ion conduction is conducive to mention Rise battery long circulating capacity retention ratio.
Comparing embodiment 1 and embodiment 10~13 increase it is found that after the materials such as the surface Al coating electron conduction graphite The electron conduction of system is conducive to promote circulating battery capacity retention ratio.Cover light (embodiment 10) mentions electron conduction Liter is unobvious, and overweight coating (embodiment 12) can be substantially reduced the lithium ion conduction property of system, and two kinds of situations are unfavorable for electricity The long-term stable circulation in pond.
As shown in Table 2, it is several can to significantly reduce the short circuit in the preparation process of solid-state lithium metal battery for embodiments herein Rate.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment Art personnel without departing from the concept of this application, can make several possible variations and modification, therefore the application Protection scope should be subject to the range that the claim of this application is defined.

Claims (10)

1. a kind of rigid membrance, which is characterized in that the rigid membrance is set to the solid electrolyte film of solid-state lithium metal battery Between piece and anode pole piece, the material of the rigid membrance in metallic element, the alloy containing the metallic element extremely Few one kind；
The metallic element can form alloy with lithium.
2. rigid membrance according to claim 1, which is characterized in that the metallic element be selected from Ge, Sn, Al, Ga, In, At least one of Mg, Zn；
The alloy containing the metallic element is selected from the alloy that the metallic element and lithium are formed.
3. rigid membrance according to claim 1, which is characterized in that the rigid membrance with a thickness of 1 μm~1000 μm, Preferably 3 μm~1000 μm, more preferably 5 μm~50 μm.
4. rigid membrance according to claim 1, which is characterized in that the elasticity modulus of the rigid membrance is greater than or equal to 5GPa。
5. rigid membrance according to claim 1, which is characterized in that at least one surface of the rigid membrance is provided with Coating；
The material of the coating is selected from lithium ion conductor, electronic conductor or electronics-lithium ion mixed conductor.
6. rigid membrance according to claim 5, which is characterized in that the only one surface of the rigid membrance is provided with lithium Ion conductor coating；Or
The only one surface of the rigid membrance is provided with electronic conductor coating；Or
One surface of the rigid membrance is provided with lithium ion conductor coating, another surface of the rigid membrance is provided with Electronic conductor coating.
7. rigid membrance according to claim 6, which is characterized in that the lithium ion conductor coating with a thickness of 50nm~ 200 μm, preferably 500nm~100 μm；
The electronic conductor coating with a thickness of 10nm~200 μm, preferably 50nm~50 μm.
8. rigid membrance according to claim 5, which is characterized in that the lithium ion conductor be selected from can embedding oxidate for lithium, At least one of simple substance coating, copolymer solid electrolyte, sulfide solid electrolyte, solid oxide electrolyte；
It is described can embedding oxidate for lithium be selected from SiO, Fe2O3、CuO、TiO2、MnO2、SnO、SnO2At least one of；
The material of the simple substance coating is selected from least one of Al, In, Mg, Sn, Ge, Si, C, Pb, Sb, Bi；
The copolymer solid electrolyte includes polymer body and lithium salts, the polymer body be selected from polyether-based polymers, At least one of polyolefin polymers, polynitriles quasi polymer, polycarboxylate quasi polymer, the lithium salts are 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；Preferably, the polymer The mass ratio of ontology and the lithium salts is 20~80:80~20；Preferably, the polyether-based polymers be selected from polyethylene oxide, At least one of polypropylene oxide, polyethylene glycol, polyethylene glycol dimethyl ether, polysiloxanes；The polyolefin polymers choosing From polyethylene, polypropylene, gather inclined tetrafluoroethene, Kynoar-hexafluoropropylene copolymer, polytetrafluoroethylene (PTFE), in polyvinyl chloride At least one；The polynitriles quasi polymer is selected from least one of polyacrylonitrile, poly- Melamine；The polycarboxylic acids esters Polymer is selected from least one of polymethyl methacrylate, polymethyl acrylate；The polycarbonate polymer is selected from At least one of polypropylene carbonate, poly- ethylenecarbonate；Preferably, the fast lithium ion conductor of the oxide is selected from and has The compound of NASICON structure, the compound with garnet structure, has perovskite at the compound with LISICON structure At least one of compound of structure；Preferably, the fast lithium ion conductor of the sulfide is selected from yLi2S-(100-y)P2S5With MS2Or the mixture of LiqQ, wherein 1 < y < 100, M are selected from Si, Ge, Sn, and Q is selected from F, Cl, Br, I, O, N, PO4 3-、SO4 2-、 BO3 3-、SiO4 4-、PF6 -、(FSO2)N-、(CF3SO2)N-, q be 1~4 integer；
The sulfide solid electrolyte is selected from yLi2S-(100-y)P2S5With MS2Or the mixed system of LiqQ, wherein 1 < y < 100, M are selected from Si, Ge, Sn, and Q is selected from F, Cl, Br, I, O, N, PO4 3-、SO4 2-、BO3 3-、SiO4 4-、(FSO2)N-、(CF3SO2)N-, q For 1~4 natural number；
The solid oxide electrolyte be selected from the compound with NASICON structure, the compound with LISICON structure, At least one of compound with garnet structure, compound with perovskite structure；It is described that there is NASICON structure The preferred LiM of compound2(PO4)3, M is selected from Ti, Zr or Ge；The preferred Li of compound with LISICON structure14Zn(GeO4)4； The preferred Li of compound with garnet structure7La3M2O12, M is selected from transition metal, more preferable Zr or Sn；With perovskite structure The preferred Li of compound3xLa1-3xTiO3, 0 < x < 0.16.
9. rigid membrance according to claim 5, which is characterized in that the electronic conductor be selected from conductive black, acetylene black, At least one of vapor-grown carbon fibers, carbon nanotube, graphite, hard carbon, soft carbon, carbonaceous mesophase spherules, graphene.
10. a kind of solid-state lithium metal battery, which is characterized in that the solid-state lithium metal battery includes cathode sheet, solid electrolytic Plasma membrane piece and anode pole piece are arranged any just like claim 1~9 between the solid electrolyte diaphragm and the anode pole piece Rigid membrance described in；
Preferably, the solid-state lithium metal battery be it is stacked, when be provided on the only one surface of the rigid membrance lithium from When sub- conductor coatings, the one of the lithium ion conductor coating is provided on the rigid membrance facing towards the adjacent anode pole Piece or towards the adjacent solid electrolyte diaphragm；It is applied when being provided with electronic conductor on the only one surface of the rigid membrance The one of the electronic conductor coating is provided with when layer, on the rigid membrance facing towards the adjacent anode pole piece；When described It is described rigid when one surface of rigid membrance is provided with lithium ion conductor coating, another surface is provided with electronic conductor coating It is provided with the one of the electronic conductor coating on property diaphragm facing towards the adjacent anode pole piece, is arranged on the rigid membrance Have the one of the lithium ion conductor coating facing towards the adjacent solid electrolyte diaphragm.
CN201710948057.8A 2017-10-12 2017-10-12 Rigid diaphragm and solid-state lithium metal battery Pending CN109659474A (en)

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Application publication date: 20190419