CN110212160A - A kind of solid state battery ion transport layers and preparation method thereof and solid state battery - Google Patents

A kind of solid state battery ion transport layers and preparation method thereof and solid state battery Download PDF

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Publication number
CN110212160A
CN110212160A CN201910562419.9A CN201910562419A CN110212160A CN 110212160 A CN110212160 A CN 110212160A CN 201910562419 A CN201910562419 A CN 201910562419A CN 110212160 A CN110212160 A CN 110212160A
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solid state
state battery
lithium
ion transport
transport layers
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颜廷房
朱蕾
汤卫平
吴勇民
吴晓萌
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Shanghai Institute of Space Power Sources
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Shanghai Institute of Space Power Sources
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides a kind of solid state battery ion transport layers and preparation method thereof and solid state battery.The ion transport layers generate high viscosity using polymer material, and it adds macroion transmission material and generates high ionic conductivity, and the interface ion transport layer of sub-micron to micron thickness is formed in situ on electrode plates by transport layer precursor solution, realize that the high strength bond at the interface of solid electrolyte film and positive and negative electrode and fast ion are transmitted.The transport layer prevents the removing in charge and discharge process between solid electrolyte film and positive and negative anodes, the electrochemical impedance controlled between solid solid interface is promoted, in addition it can buffer positive and negative anodes volume change in charge and discharge process, effectively inhibit in composite solid electrolyte to the interface side reaction between lithium loose material and lithium metal.The present invention includes above-mentioned ion transport layers material and preparation method thereof and the solid state battery using the ion transport layers.

Description

A kind of solid state battery ion transport layers and preparation method thereof and solid state battery
Technical field
The present invention relates to a kind of solid state battery ion transport layers and preparation method thereof and solid state batteries.
Background technique
Lithium battery is widely regarded as most promising next-generation rechargeable energy stores due to its high-energy density Device.But since there are the safety issues such as inflammable, perishable and thermal stability is poor for organic electrolyte, make conventional lithium ion The development of battery is restricted.Cause increasingly due to solid electrolyte safety problem caused by it can solve liquid electrolyte More concerns.
Solid state lithium battery has security performance height, has extended cycle life, operating temperature range compared to conventional lithium ion battery The advantages that wide.But since solid electrolyte electric conductivity is low, mechanical stability difference and higher electrode/electrolyte interface impedance, limit The practical application of full lithium state battery admittedly is made.Qualified solid lithium battery should have a following characteristic: first, solid electrolyte Lithium ion conductivity should be greater than 10-4S cm-1；Second, there are stable small impedance interfaces between electrolyte and electrode；Third, tool There are certain mechanical strength and flexible solid electrolyte to can control lithium dendrite growth and buffers electrode material in charge and discharge process The volume change of material.
As solid state battery core component --- solid electrolyte is to realize solid state battery high-energy density, high circulation The critical material of stability and high safety performance.Wherein due to intensity height, electrochemical window and high ionic conductivity are excellent, are based on The composite solid electrolyte of Kynoar (PVDF) or Kynoar-hexafluoropropene (PVDF-HFP) (it is multiple to be denoted as PVDF base Close solid electrolyte) be present lithium cell electrolyte one of research hotspot.
But when PVDF base composite solid electrolyte is used for solid state battery, due to matrix used compared to polycyclic oxygen second Alkane (PEO) hardness is big, viscoelasticity is low, poor to lithium stabilization, therefore electrode/electrolyte interface connects compared with PEO base composite solid electrolyte It is poor to touch, and the volume change of electrode material in charge and discharge process can not be preferably buffered, and because it is poor to the compatibility of lithium, with lithium When metal is as cathode, it is easy to that side reaction occurs with lithium metal, so that the performance for seriously affecting solid state battery plays.
Summary of the invention
Technology of the invention solves the problems, such as: providing a kind of solid state battery ion transport layers, the ion transport layers are set It sets between the anode and composite solid electrolyte of solid state battery and between cathode and composite solid electrolyte, can reduce solid Liquid/solid interface impedance buffers the volume change of electrode material in charge and discharge process, and effectively inhibits composite solid electrolyte and electrode Between side reaction.
The technical solution of the invention is as follows: a kind of solid state battery ion transport layers, including polyethylene oxide and it is high from The mass ratio of sub- transmission material, the polyethylene oxide and macroion transmission material is (1~3): (0.5~2).
Preferably, the macroion transmission material includes lithium salts, ionic liquid, at least one in organic film for additive Kind.
Preferably, the lithium salts is LiTFSI, LiFSI, LiClO4、LiPF6、LiBF4、LiBOB、LiDFOB、LiPF2O2In One kind.
Preferably, the ionic liquid is 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt C8H11F6N3O4S2。
Preferably, organic film for additive is ethylene carbonate EC, fluorinated ethylene carbonate FEC, sulfurous acid butylene Ester BS, diethyl carbonate DEC, dimethyl sulfite DMS, ethylene sulfite ES, propylene sulfite PS, vinylene carbonate At least one of ester VC and diethyl sulfite DES.
The present invention provides a kind of solid state battery ion transport layers and preparation method thereof, wherein the method includes:
Step 1: by polyethylene oxide and macroion transmission material respectively according to 0.01-0.03g/mL and 0.005-0.02g/ The concentration of mL is dissolved in solvent, and 50-70 DEG C of stirring forms transport layer precursor solution；
Step 2: resulting transport layer precursor solution is coated uniformly on electrode plates surface, drying at room temperature, in pole piece One layer of stickiness ion transport layers of upper formation.
Preferably, the solvent is one of acetonitrile or dimethyl carbonate.
The volume of the transport layer precursor solution being coated uniformly on electrode slice is 0.05-0.15mL/cm2。
The present invention provides a kind of solid state battery containing ion transport layers, including it is anode layer, stickiness ion transport layers, organic Inorganic compounding solid electrolyte membrane, negative electrode layer.Anode layer and PVDF base composite solid electrolyte layer and negative electrode layer and PVDF base Above-mentioned transport layer is equipped between composite solid electrolyte layer.
The above-mentioned solid state battery containing ion transport layers, the anode layer include active material, conductive agent, binder and Lithium salts, mass ratio of each component are (75-80): (8-10): (8-10): (3-5).The active material be cobalt acid lithium, LiMn2O4, One of LiFePO4, nickel-cobalt-manganese ternary material and nickel cobalt aluminium ternary material.The conductive agent is carbon nano-fiber, SuperP, acetylene black, electrically conductive graphite KS6, one of carbon nanotube or graphene.The binder is Kynoar. The lithium salts is bis trifluoromethyl sulfimide lithium (LiTFSI), double fluorine sulfimide lithiums (LiFSI), lithium perchlorate (LiClO4), lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), dioxalic acid lithium borate (LiBOB), oxalic acid difluoro boric acid Lithium (LiDFOB), difluorophosphate (LiPF2O2One of).
The ion transport layers include polyethylene oxide and macroion transmission material, the macroion transmission material packet Include at least one of lithium salts, ionic liquid, organic film for additive.The lithium salts is LiTFSI, LiFSI, LiClO4、 LiPF6、LiBF4、LiBOB、LiDFOB、LiPF2O2One of.The ionic liquid is 1- ethyl-3-methylimidazole double three Fluorine sulfonamide (C8H11F6N3O4S2).Organic film for additive is ethylene carbonate (EC), fluoro ethylene carbonate Ester (FEC), butylene sulfite (BS), diethyl carbonate (DEC), dimethyl sulfite (DMS), ethylene sulfite (ES), at least one of propylene sulfite (PS), vinylene carbonate (VC) and diethyl sulfite (DES).
The organo-mineral complexing solid electrolyte membrane includes high molecular polymer matrix, lithium salts and inorganic filler, respectively Composition quality ratio is (3-4): 1:(0.5-1).The high molecular polymer is Kynoar or Kynoar-hexafluoropropene One of copolymer.The lithium salts is LiTFSI, LiFSI, LiClO4、LiPF6、LiBF4、LiBOB、LiDFOB、LiPF2O2 One of.The inorganic filler is Al2O3、SiO2、MgO、Li7La3Zr2O12(LLZO)、Li6.4La3Zr1.4Ta0.6O12 (LLZTO) or Li1.4Al0.4Ti1.6(PO4)3(LATP) and Li1.5Al0.5Ge1.5(PO4)3One of (LAGP).
The negative electrode layer is lithium metal or the composite negative pole being prepared by one of lithium titanate, silicon-carbon or graphite.
The present invention has the beneficial effect that compared with prior art
(1) ion transport layers of the present invention generate high viscosity using polymer material, and add the generation of macroion transmission material High ionic conductivity, and sub-micron is formed in situ to the interface of micron thickness on electrode plates by transport layer precursor solution Ion transport layers realize that the high strength bond at the interface of solid electrolyte film and positive and negative electrode and fast ion are transmitted.The transmission Layer prevents the removing in charge and discharge process between solid electrolyte film and positive and negative anodes, controls the electrochemistry resistance between solid solid interface Anti- promotion effectively inhibits in composite solid electrolyte to lithium in addition it can buffer positive and negative anodes volume change in charge and discharge process Interface side reaction between loose material and lithium metal.
(2) transport layer of the invention has better compatibility with lithium metal using polyethylene oxide as main component, When using lithium anode, is added between PVDF base composite solid electrolyte film and cathode of lithium, battery can be inhibited Side reaction between middle solid electrolyte and lithium metal inhibits the generation of Li dendrite, keeps the stability at interface.
(3) using film for additive as auxiliary material, film for additive adds the part formulation of transport layer of the invention Enter to can effectively improve the ionic conductivity of transport layer, and a small amount of film for additive helps to be formed in charge and discharge process Stable SEI film.
(4) transport layer of the invention has soft structure and certain ionic conductivity.By transport layer setting in solid-state electricity Between pond electrode and PVDF base composite solid electrolyte, relatively hard solid solid interface can be converted to softer interface, dropped Low interface stress reduces interface impedance.
(5) well contacting for pole piece and solid electrolyte membrane may be implemented in transport layer of the invention, due to the transmission of formation Layer has excellent viscoelasticity compared with PVDF base solid electrolyte membrane, therefore can effectively buffer electrode material in charge and discharge process The volume change of material prevents gap enlargement at electrode/electrolyte interface.
(6) raw material of stickiness ion transport layers of the invention is easy to get, at low cost, and preparation process easily magnifies.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of solid state battery of the present invention.
Fig. 2 is the impedance diagram of lithium Symmetrical cells prepared by the embodiment of the present invention 1.
Fig. 3 is the impedance diagram of solid state battery prepared by the embodiment of the present invention 1.
Fig. 4 is the anode pole piece section SEM photograph containing ion transport layers prepared by the embodiment of the present invention 2.
Fig. 5 is the cycle performance curve of solid state battery prepared by the embodiment of the present invention 3.
Fig. 6 is the dissection material object photo figure after 5 circle of the circulation of solid state battery prepared by the embodiment of the present invention 3.
Fig. 7 is the anode pole piece scanning electron microscope (SEM) photograph after 100 circle of the circulation of solid state battery prepared by the embodiment of the present invention 3.
Specific embodiment
With reference to the accompanying drawing and example elaborates to the present invention.
As shown in Figure 1, being a kind of internal structure of solid state battery provided by the invention, the battery main body is by anode pole piece 1 (also known as anode layer), stickiness ion transport layers 2, PVDF base composite solid electrolyte layer 3, stickiness ion transport layers 4 and cathode pole Piece 5 (also known as negative electrode layer) stacks gradually to be formed.
The anode layer includes active material, conductive agent, binder and lithium salts.The active material be cobalt acid lithium, One of LiMn2O4, LiFePO4, nickel-cobalt-manganese ternary material and nickel cobalt aluminium ternary material.The conductive agent is Nano carbon fibers Dimension, SuperP, acetylene black, electrically conductive graphite KS6, one of carbon nanotube or graphene.The binder is polyvinylidene fluoride Alkene.The lithium salts is bis trifluoromethyl sulfimide lithium LiTFSI, double fluorine sulfimide lithium LiFSI, lithium perchlorate LiClO4, six Lithium fluophosphate LiPF6, LiBF4 LiBF4, dioxalic acid lithium borate LiBOB, LiODFB LiDFOB, difluorophosphoric acid Lithium LiPF2O2One of.
The stickiness ion transport layers include polyethylene oxide and macroion transmission material, and the macroion transmits material Material includes at least one of lithium salts, ionic liquid, organic film for additive.The lithium salts be LiTFSI, LiFSI, LiClO4、LiPF6、LiBF4、LiBOB、LiDFOB、LiPF2O2One of.The ionic liquid is 1- ethyl -3- methyl miaow Azoles bis-trifluoromethylsulfoandimide salt C8H11F6N3O4S2.Organic film for additive is ethylene carbonate EC, fluoro carbonic acid second Enester FEC, butylene sulfite BS, diethyl carbonate DEC, dimethyl sulfite DMS, ethylene sulfite ES, sulfurous acid At least one of acrylic ester PS, vinylene carbonate VC and diethyl sulfite DES.
The organo-mineral complexing solid electrolyte membrane includes high molecular polymer matrix, lithium salts and inorganic filler.Institute Stating high molecular polymer is one of Kynoar or Kynoar-hexafluoropropylene copolymer.The lithium salts is LiTFSI、LiFSI、LiClO4、LiPF6、LiBF4、LiBOB、LiDFOB、LiPF2O2One of.The inorganic filler is Al2O3、SiO2、MgO、Li7La3Zr2O12(LLZO)、Li6.4La3Zr1.4Ta0.6O12(LLZTO) or Li1.4Al0.4Ti1.6(PO4)3 (LATP) and Li1.5Al0.5Ge1.5(PO4)3One of (LAGP).
The negative electrode layer is lithium metal or the composite negative pole being prepared by one of lithium titanate, silicon-carbon or graphite.
The solid state battery intermediate ion transport layer is present between electrode and PVDF base composite solid electrolyte, and electricity may be implemented Pole is well contacted with dielectric film, is reduced interfacial stress, is reduced interface impedance, while effectively inhibiting solid electrolyte membrane and electricity Side reaction between pole effectively improves active material utilization, improves capacity and efficiency for charge-discharge.
The present invention it is specific the preparation method is as follows:
(1) prepared by anode pole piece
Step 1: binder, conductive agent, positive electrode active materials and lithium salts are successively added according to mass ratio 10:10:77:3 It is added in nmp solvent and carries out dispersion stirring, obtain anode sizing agent；Step 2: anode sizing agent is coated on by aluminium foil using coating machine On, the drying temperature of coating machine is 120 DEG C, and the pole piece after winding is dried for 24 hours, after drying in 100 DEG C of vacuum drying oven Electrode slice carries out roll-in, and punching obtains anode pole piece；
(2) prepared by composite negative pole pole piece
Binder, conductive agent, negative electrode active material and lithium salts are successively added to NMP according to mass ratio 10:10:77:3 Dispersion stirring is carried out in solvent, obtains negative electrode slurry；Step 2: anode sizing agent being coated on copper foil using coating machine, coating machine Drying temperature be 120 DEG C, pole piece after winding in 100 DEG C of vacuum drying oven it is dry for 24 hours, the electrode slice after drying is carried out Roll-in, punching obtain cathode pole piece；
(3) preparation of ion transport layers
Step 1: by polyethylene oxide and macroion transmission material respectively according to 0.01~0.03g/mL and 0.005~ The concentration of 0.02g/mL is dissolved in volatile solvent, and 50-70 DEG C of stirring forms transport layer precursor solution；Step 2: by transport layer Precursor solution presses 0.05~0.15mL/cm2Dosage, be coated uniformly on electrode slice surface, exist after the 6-8h that volatilizees under room temperature Stickiness ion transport layers are formed on electrode slice.
(4) preparation of solid state battery
Successively by the anode pole piece 1 containing transport layer, PVDF base composite solid electrolyte layer 3, the cathode pole containing transport layer Piece 5 inserts button cell stainless steel case by the way of stacking, and button cell is assembled into glove box and is tested.
In order to further decrease impedance, behaviour can be reheated in 50-70 DEG C of progress 1-2h after above-mentioned composition completes battery Make, is tested after being cooled to room temperature.
A specific embodiment of the invention is further described with attached drawing with reference to embodiments.
Embodiment 1:
(1) prepared by anode pole piece
Step 1: binder PVDF, conductive agent SuperP, positive electrode active materials LiFePO4With lithium salts LiClO4In mass ratio 10:10:77:3, which is successively added in nmp solvent, carries out dispersion stirring, obtains anode sizing agent；Step 2: will be positive using coating machine Slurry is coated on aluminium foil, and the drying temperature of coating machine is 120 DEG C, and the pole piece after winding is dry in 100 DEG C of vacuum drying oven For 24 hours, roll-in is carried out to the electrode slice after drying, punching obtains anode pole piece；
(2) preparation of ion transport layers
Step 1: 0.24g polyethylene oxide and 0.1g ethylene carbonate being dissolved in 15mL dimethyl carbonate solvent, 60 DEG C Heating stirring forms stickiness ion transport layers precursor solution to transparent；Step 2: 0.12mL precursor solution is uniformly coated In LiFePO4Positive plate and lithium anode surface stand 8h under room temperature, are formed on electrode slice after solvent volatilizees completely Transport layer.
(3) preparation of solid state battery
Successively by the anode pole piece 1 containing transport layer, PVDF base composite solid electrolyte layer 3, the cathode pole containing transport layer Piece 5 (lithium metal) inserts button cell stainless steel case by the way of stacking, and button cell is assembled into glove box and is carried out Test.
Lithium metal Symmetrical cells impedance diagram such as Fig. 2 institute handled by 1 containing stickiness ion transport layers through this embodiment Show, compared with the Symmetrical cells without transport layer, the impedance in PVDF base solid electrolyte membrane is substantially reduced, and illustrates metal Interfacial contact and compatibility between lithium and PVDF base solid electrolyte membrane are improved.
The impedance before the solid state battery circulation prepared by 1 containing ion transport layers is as shown in figure 3, by it through this embodiment Compared with the solid state battery without transport layer, impedance has been down to 90 Ω by 645 Ω, and impedance reduces obvious, it was demonstrated that the biography of lithium ion Movement Capabilities enhancing, chemical property improve.
Embodiment 2:
(1) prepared by anode pole piece
Step 1: by binder PVDF, conductive agent SuperP, positive electrode active materials LiNi0.5Co0.2Mn0.3O2And lithium salts LiClO4Successively it is added in nmp solvent in mass ratio and carries out dispersion stirring, obtains anode sizing agent；Step 2: using coating machine will Anode sizing agent is coated on aluminium foil, and the drying temperature of coating machine is 120 DEG C, and the pole piece after winding is in 100 DEG C of vacuum drying oven Drying carries out roll-in for 24 hours, to the electrode slice after drying, and punching obtains anode pole piece；
(2) prepared by composite negative pole pole piece
Step 1: by binder PVDF, conductive agent SuperP, negative electrode active material graphite and lithium salts LiClO4In mass ratio Successively it is added in nmp solvent and carries out dispersion stirring, obtains negative electrode slurry；Step 2: being coated on negative electrode slurry using coating machine On copper foil, the drying temperature of coating machine is 120 DEG C, and the pole piece after winding is dried in 100 DEG C of vacuum drying oven for 24 hours, to drying Electrode slice afterwards carries out roll-in, and punching obtains cathode pole piece；
(3) preparation of ion transport layers
Step 1: by 0.24g polyethylene oxide, 0.1g ethylene carbonate, 0.06gLiTFSI is dissolved in 12mL acetonitrile solvent, 60 DEG C of heating stirrings form stickiness ion transport layers precursor solution to transparent；Step 2: 0.12mL precursor solution is uniform Coated in LiNi0.5Co0.2Mn0.3O2Positive plate and graphite cathode piece surface, after standing 8h under room temperature, after solvent volatilizees completely Transport layer is formed on electrode slice.
(4) preparation of lithium solid state battery
Successively by the anode pole piece 1 containing transport layer, PVDF base composite solid electrolyte layer 3, the cathode pole containing transport layer Piece 5 inserts button cell stainless steel case by the way of stacking, and button cell is assembled into glove box and is tested.
The anode pole piece section SEM photograph prepared by 2 containing ion transport layers is as shown in figure 4, as schemed through this embodiment Shown, the ion transport layers being covered on anode pole piece contact closely with positive electrode particle, and buffer layer thickness is micron order or less.
Embodiment 3:
(1) prepared by anode pole piece
Step 1: by binder PVDF, conductive agent SuperP, positive electrode active materials LiNi0.5Co0.2Mn0.3O2And lithium salts LiClO4Successively it is added in nmp solvent in mass ratio and carries out dispersion stirring, obtains anode sizing agent；Step 2: using coating machine will Anode sizing agent is coated on aluminium foil, and the drying temperature of coating machine is 120 DEG C, and the pole piece after winding is in 100 DEG C of vacuum drying oven Drying carries out roll-in for 24 hours, to the electrode slice after drying, and punching obtains anode pole piece；
(2) preparation of ion transport layers
Step 1: 0.24g polyethylene oxide and 0.1g ethylene carbonate being dissolved in 15mL dimethyl carbonate solvent, 60 DEG C Heating stirring forms stickiness ion transport layers precursor solution to transparent；Step 2: 0.12mL precursor solution is uniformly coated In LiNi0.5Co0.2Mn0.3O2Positive plate and metallic lithium surface are in electrode after solvent volatilize completely after standing 8h under room temperature On piece forms transport layer.
(3) preparation of solid state battery
Successively by the anode pole piece 1 containing transport layer, PVDF base composite solid electrolyte layer 3, the cathode pole containing transport layer Piece 5 (lithium metal) inserts button cell stainless steel case by the way of stacking, and button cell is assembled into glove box and is carried out Test.
Through this embodiment solid state battery prepared by 3 charging and discharging curve as shown in figure 5, battery with the electric current of 15mA/g Density carries out charge and discharge cycles in 2.8~4.3V voltage range at room temperature, and first discharge specific capacity 152.6mAh/g is higher than The solid state battery and liquid lithium ionic cell performance of conventional PVDF base composite solid electrolyte film are suitable, and hold after recycling 100 circles It measures conservation rate and is greater than 92%.
The dissection material object photo after 5 circle of the circulation of solid state battery prepared by 3 is as shown in fig. 6, A is not add through this embodiment Add the solid state battery of transport layer, B is the solid state battery for adding transport layer.As can be seen that addition transport layer can guarantee that battery follows Good contact during ring.Fig. 7 is the positive pole that solid state battery prepared by 3 recycles after 100 circles through the embodiment of the present invention The scanning electron microscope (SEM) photograph of piece, A are the anode pole piece for not adding transport layer, and B is the anode pole piece for adding transport layer.As can be seen that not There are a large amount of crackles with the presence of the electrode slice surface of transport layer covering, and has the electrode slice surface of transport layer very complete, it is not bright Aobvious crackle, this illustrates the cubic deformation that the presence of transport layer can inhibit electrode material to generate in charge and discharge process.
In conclusion when using PVDF class material as composite solid electrolyte matrix, due to such material hardness itself It is larger, viscoelasticity is lower, poor to the compatibility of lithium, the solid state battery interface impedance of assembling is big, can not effectively buffer charge and discharge The volume change of positive and negative anodes in the process, and interface side reaction easily occurs in negative side, lead to battery failure.In view of this, this hair It is bright to start with from electrode/electrolyte interface, it is transmitted with the excellent viscoelasticity of PEO class material and to lithium stability combination macroion Material provides a low-impedance stable interface for PVDF base solid state battery, to effectively improve the performance of battery.
Ion transport layers of the invention are applied to LiNi0.5Co0.2Mn0.3O2It is solid for the PVDF base of positive active material In state battery, first discharge specific capacity can achieve 152.6mAh/g, and after circulation 100 is enclosed, capacity retention ratio is greater than 92%, height In the solid state battery of conventional PVDF base composite solid electrolyte, it is expected to be answered in the fields such as accumulation power supply and power battery With.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Unspecified part of the present invention belongs to common sense well known to those skilled in the art.

Claims (14)

1. a kind of solid state battery ion transport layers, which is characterized in that described including polyethylene oxide and macroion transmission material Polyethylene oxide and macroion transmission material mass ratio be (1~3): (0.5~2).
2. a kind of solid state battery ion transport layers as described in claim 1, which is characterized in that the macroion transmission material Including at least one of lithium salts, ionic liquid, organic film for additive.
3. macroion transmission material as claimed in claim 2, which is characterized in that the lithium salts be LiTFSI, LiFSI, LiClO4、LiPF6、LiBF4、LiBOB、LiDFOB、LiPF2O2One of.
4. a kind of macroion transmission material as claimed in claim 2, which is characterized in that the ionic liquid is 1- ethyl -3- Methylimidazole bis-trifluoromethylsulfoandimide salt C8H11F6N3O4S2。
5. macroion transmission material as claimed in claim 2, which is characterized in that organic film for additive is ethylene carbonate Ester EC, fluorinated ethylene carbonate FEC, butylene sulfite BS, diethyl carbonate DEC, dimethyl sulfite DMS, sulfurous acid At least one of vinyl acetate ES, propylene sulfite PS, vinylene carbonate VC and diethyl sulfite DES.
6. a kind of preparation method of solid state battery ion transport layers, it is characterised in that steps are as follows:
Step 1: by polyethylene oxide and macroion transmission material respectively according to 0.01~0.03g/mL and 0.005~0.02g/mL Concentration be dissolved in volatile solvent, 50-70 DEG C stirring, obtain uniform transport layer precursor solution；The volatile solvent For one of acetonitrile (ACN) or dimethyl carbonate (DMC)；
Step 2: resulting transport layer precursor solution being coated uniformly on positive and negative anodes pole piece, 6-8h is dried at room temperature, in pole On piece forms one layer of stickiness ion transport layers, obtains the pole piece of transport layer modification.
7. according to the method described in claim 6, it is characterized by: in step 2 transport layer precursor solution dosage be 0.05~ 0.15mL/cm2。
8. a kind of solid state battery of ion transport layers containing solid state battery, which is characterized in that including anode layer, organo-mineral complexing Ion transport layers described in one of solid electrolyte membrane, negative electrode layer and claim 1-5；The ion transport layers exist Between anode layer and organo-mineral complexing solid electrolyte membrane and negative electrode layer and organo-mineral complexing solid electrolyte membrane it Between.
9. solid state battery as claimed in claim 8, which is characterized in that the ion transport layers in-situ preparation is in anode layer, negative The surface of pole layer.
10. solid state battery as claimed in claim 8, which is characterized in that the ion transport layers are with a thickness of 100nm-1 μm.
11. solid state battery as claimed in claim 8, which is characterized in that carried out to the solid state battery being completed in 50-70 DEG C The processing of 1-2h reheating is cooled to after room temperature for testing.
12. solid state battery as claimed in claim 8, which is characterized in that the anode layer includes active material, conductive agent, glues Agent and lithium salts are tied, mass ratio of each component is (75-80): (8-10): (8-10): (3-5)；
The active material is one in cobalt acid lithium, LiMn2O4, LiFePO4, nickel-cobalt-manganese ternary material and nickel cobalt aluminium ternary material Kind；The conductive agent is carbon nano-fiber, SuperP, acetylene black, electrically conductive graphite KS6, one of carbon nanotube or graphene； The binder is Kynoar；The lithium salts be bis trifluoromethyl imine lithium LiTFSI, double fluorine sulfimide lithium LiFSI, Lithium perchlorate LiClO4, lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4, dioxalic acid lithium borate LiBOB, oxalic acid difluoro boric acid Lithium LiDFOB, difluorophosphate LiPF2O2One of.
13. solid state battery as claimed in claim 8, which is characterized in that the organo-mineral complexing solid electrolyte film packet High molecular polymer matrix, lithium salts and inorganic filler are included, mass ratio of each component is (3-4): 1:(0.5-1)；
The high molecular polymer is one of Kynoar or Kynoar-hexafluoropropylene copolymer；The lithium salts For LiTFSI, LiFSI, LiClO4、LiPF6、LiBF4、LiBOB、LiDFOB、LiPF2O2One kind；The inorganic filler is Al2O3、SiO2、MgO、Li7La3Zr2O12(LLZO)、Li6.4La3Zr1.4Ta0.6O12(LLZTO) or Li1.4Al0.4Ti1.6(PO4)3 (LATP) and Li1.5Al0.5Ge1.5(PO4)3One of (LAGP).
14. solid state battery as claimed in claim 8, which is characterized in that the negative electrode layer be lithium metal or by lithium titanate, The composite negative pole that one of silicon-carbon or graphite are prepared into.
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