CN106299467A - Composite solid electrolyte and flexible all-solid-state battery and preparation method, wearable electronic - Google Patents

Composite solid electrolyte and flexible all-solid-state battery and preparation method, wearable electronic Download PDF

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Publication number
CN106299467A
CN106299467A CN201610822459.9A CN201610822459A CN106299467A CN 106299467 A CN106299467 A CN 106299467A CN 201610822459 A CN201610822459 A CN 201610822459A CN 106299467 A CN106299467 A CN 106299467A
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China
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composite
solid electrolyte
solid
lithium
electrolyte
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Inventor
南策文
陈儒君
张益博
刘亭
林元华
沈洋
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Tsinghua University
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Tsinghua University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0085Immobilising or gelification of electrolyte
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention proposes composite solid electrolyte and preparation method thereof, flexible all-solid-state battery and preparation method thereof and wearable electronic.This composite solid electrolyte contains: ceramic base solid electrolyte and the first polymer-based solid state electrolyte;Wherein, gross weight based on this composite solid electrolyte, the content of ceramic base solid electrolyte is 20~90 weight %.Composite solid electrolyte proposed by the invention, there is high ion conductivity, good heat stability and the electrochemical stability under good mechanical performance, room temperature, safety is high, can be effectively prevented and be penetrated by Li dendrite, also and between anode composite, form good interracial contact such that it is able to obtain area ratio capacity and energy density is high, internal resistance of cell cutting high, the most bent less, flexible is without the flexible all-solid-state battery of impact use.

Description

Composite solid electrolyte and flexible all-solid-state battery and preparation method, wearable electronic Equipment
Technical field
The present invention relates to technical field of lithium ion, concrete, the present invention relates to composite solid electrolyte and preparation thereof Method, flexible all-solid-state battery and preparation method thereof and wearable electronic.
Background technology
At present, commercial li-ion battery many employings liquid electrolyte is as the conduction of lithium ion between positive pole and negative material Medium, but along with the requirement of lithium ion battery maximization application is more and more higher, the drawback of liquid electrolyte progressively manifests, Yin Qiyi Combustion explosion hazard, brings bigger potential safety hazard to the large-scale application of lithium ion battery.
For the problems referred to above, the use solid electrolyte traditional electrolyte of replacement prepares all-solid lithium-ion battery and is Best solution.All-solid lithium-ion battery can stop the security incidents such as leakage and blast, can meet again simultaneously A lot of harsh environments require and the condition of use.But, the design of all-solid-state battery structure remains a difficult problem, anode composite Design, positive pole and solid electrolyte between the optimization etc. at interface be all urgent problem.
Summary of the invention
It is contemplated that one of technical problem solved the most to a certain extent in correlation technique.
The present invention is following discovery based on inventor and completes:
The present inventor finds in research process, and solid electrolyte material can be divided into ceramic base solid electrolyte material and gather Compound base solid electrolyte material.Wherein, ceramic base solid electrolyte material has higher lithium ion conductive in room temperature, and There are good heat stability, an electrochemical stability, but the interface of formation good contact more difficult with positive pole so that assemble and obtain All-solid lithium-ion battery internal resistance is bigger;And polymer-based solid state electrolyte can form good contact interface with positive pole, But its mechanical strength is poor, it is possible to penetrated by Li dendrite.
The present inventor finds through further investigation, and solid electrolyte is based on ceramic base solid electrolyte, machine Tool intensity is high, nonflammable non-explosive, and safety is high;Meanwhile, add in anode composite and solid electrolyte a certain proportion of Polymer based electrolyte material, it is possible to improve the ion transmission performance of anode composite and anode composite and solid electrolyte Interface, moreover it is possible to make all-solid lithium-ion battery have certain flexibility, bends it, cuts all without affecting all-solid-state battery Use.
In view of this, it is an object of the present invention to propose a kind of there is macroion under good mechanical performance, room temperature Electrochemical stability bent under electric conductivity, excellent area ratio capacity, excellent energy density, good heat stability, high temperature The flexible all-solid-state battery of cutting.
In a first aspect of the present invention, the present invention proposes a kind of composite solid electrolyte.According to embodiments of the invention, Described composite solid electrolyte contains: ceramic base solid electrolyte;With the first polymer-based solid state electrolyte;Wherein, based on institute Stating the gross weight of composite solid electrolyte, the content of described ceramic base solid electrolyte is 20~90 weight %;Optionally, based on The gross weight of described composite solid electrolyte, the content of described ceramic base solid electrolyte is 40~80 weight %, described first The content of polymer-based solid state electrolyte is 20~60 weight %.
The present inventor finds through long-term research, compound all solid state based on ceramic base solid electrolyte In electrolyte, after adding polymer-based solid state electrolyte, mechanical performance can be improved significantly, and can be effectively prevented lithium Dendrite penetrates electrolyte, is combined all solid state electrolyte simultaneously and has again certain flexibility, also can be formed good with anode composite Interface.
The present inventor furthers investigate discovery, and the content of ceramic base solid electrolyte is the total of composite solid electrolyte During 20~90 weight % of weight, it is possible to ensure that composite solid electrolyte has good mechanical performance and with compound simultaneously Positive pole forms good interface, further has flexibility, and bent, cutting is without affecting serviceability.Concrete, pottery The content of base solid electrolyte be the content of 40~80 weight % and the first polymer-based solid state electrolyte be 20~60 weight % Time, composite solid electrolyte can have high mechanical strength and good interface, and more excellent flexibility the most simultaneously, Can arbitrarily bend.
Inventor it was unexpectedly observed that use the composite solid electrolyte of the embodiment of the present invention, have good mechanical performance, High ion conductivity under room temperature, good heat stability and electrochemical stability, can be effectively prevented and be penetrated by Li dendrite, also And forming good interracial contact between anode composite, safety is high.
It addition, composite solid electrolyte according to the above embodiment of the present invention, it is also possible to there is following additional technology special Levy:
According to embodiments of the invention, described ceramic base solid electrolyte includes selected from lithium lanthanum zirconium oxygen, Li-La-Ti oxygen, phosphoric acid At least one of titanium aluminum lithium and phosphoric acid germanium aluminum lithium.The present inventor finds through research, and lithium lanthanum zirconium oxygen is cubic garnet Structure, has higher room-temperature ion conductivity and electrochemical stability, can optimize the interface improving between electrode and electrolyte Contact;The room temperature crystal grain electrical conductivity of Li-La-Ti oxygen is the highest, and its electrical conductivity is closest to commercial level;And titanium phosphate aluminum lithium belongs to Trigonal system, has higher room-temperature ion conductivity, close to business level of electrolyte.
Thus, use the ceramic base solid electrolyte of the embodiment of the present invention, at room temperature have higher ionic conductivity, and And have good heat stability and electrochemical stability, the total solids that can be prepared by high-mechanical property is processed without high temperature sintering Battery.
According to embodiments of the invention, described first polymer-based solid state electrolyte includes: the first lithium salts, described lithium salts bag Include selected from lithium perchlorate, trifluoromethane sulfonic acid amine lithium, lithium hexafluoro phosphate, LiBF4 and at least the one of diacetic acid Lithium biborate Kind;And first macromolecule matrix, described macromolecule matrix includes selected from polyethylene glycol oxide or its modifier, polymethylacrylic acid Methyl ester or its modifier, Kynoar or its modifier, polyacrylonitrile or its modifier and chlorohydrin rubber or its modifier At least one.
The present inventor finds through research, and the energy density of polymer solid base electrolyte is high, manufacture easy, peace Complete reliable also flexible design, and good contact interface, meanwhile, above-mentioned height between polymeric material and anode composite, can be formed The toughness of molecular matrix is high, and the flexibility of the composite solid electrolyte lamella of formation is improved.Further, add in macromolecule matrix Add lithium salts, the ion transmission performance of polymer solid base electrolyte can be improved, strengthen the mechanical strength of macromolecule matrix.
Thus, use the polymer-based solid state electrolyte of the embodiment of the present invention, there is higher toughness, with ceramic base solid-state Mechanical performance and the flexibility of the solid electrolyte after electrolyte is compound are promoted the most significantly, are formed good with positive pole simultaneously Contact interface, thus reduce the internal resistance of all-solid-state battery.
In a second aspect of the present invention, the present invention proposes a kind of flexible all-solid-state battery.Enforcement according to the present invention Example, this flexibility all-solid-state battery contains above-mentioned composite solid electrolyte.It will be appreciated to those of skill in the art that this flexibility is complete Solid state battery no longer can also repeat at this containing the parts of other necessity, such as positive pole, negative pole etc..
Inventor, it was unexpectedly observed that use the flexible all-solid-state battery of the embodiment of the present invention, can at high temperature use, machinery Intensity is high, and security performance is good, has area ratio capacity and the energy density of excellence, and the internal resistance of cell is less, and it is flexible high, Bent, cutting without the use affecting all-solid-state battery.It will be appreciated to those of skill in the art that above for compound Feature and advantage described by solid electrolyte, are still applied to this flexibility all-solid-state battery, do not repeat them here.
It addition, flexible all-solid-state battery according to the above embodiment of the present invention, it is also possible to there is following additional technology special Levy:
According to embodiments of the invention, this flexibility all-solid-state battery is possibly together with anode composite and negative pole;Based on described compound The gross weight of positive pole, described anode composite includes: positive active material, and its content is 40~90 weight %, it is preferable that 50~75 Weight %;Second polymer-based solid state electrolyte, its content is 5~40 weight %, it is preferable that 20 weight %;Add with conduction Agent, its content is 5~30 weight %.
Inventor is it was unexpectedly observed that add a certain proportion of polymer-based solid state electrolyte in anode composite, it is possible to change The ion transmission performance of kind anode composite, and anode composite and the interracial contact of solid electrolyte, also make anode composite also There is certain flexibility.Thus, use the anode composite of the embodiment of the present invention, ion transporting can be improved, moreover it is possible to improve electricity Sub-conductivity, has good interracial contact with solid electrolyte, and has flexibility, and make the electrical property of all-solid-state battery obtain Promote, internal resistance reduces and flexible raising.
According to embodiments of the invention, described positive active material, including selected from cobalt acid lithium, LiMn2O4, LiFePO4 and At least one of nickel-cobalt-manganese ternary material.Thus, use the positive active material of the embodiment of the present invention, anode composite can be made to have Higher electro-chemical activity, possesses charge-discharge performance, and electrochemical stability, thus increase all-solid-state battery stability and Safety.
According to embodiments of the invention, described second polymer-based solid state electrolyte contains: the second lithium salts, described lithium salts bag Include selected from lithium perchlorate, trifluoromethane sulfonic acid amine lithium, lithium hexafluoro phosphate, LiBF4 and at least the one of diacetic acid Lithium biborate Kind;With the second macromolecule matrix, described macromolecule matrix includes selected from polyethylene glycol oxide or its modifier, poly-methyl methacrylate Ester or its modifier, Kynoar or its modifier, polyacrylonitrile or its modifier and chlorohydrin rubber or its modifier are extremely Few one.Thus, use the polymer-based solid state electrolyte of the embodiment of the present invention, there is higher toughness, carry for anode composite Macroion transmission channel, thus increase the ion transporting of anode composite, moreover it is possible to increase anode composite and composite solid electrolyte Between contact interface, thus reduce all-solid-state battery internal resistance, improve all-solid-state battery electro-chemical activity.
According to embodiments of the invention, described conductive additive, including selected from tin indium oxide, Indium sesquioxide., tin ash, oxygen Change zinc, nickel oxide, ferroso-ferric oxide, conductive carbon black, electrically conductive graphite, CNT, Graphene, carbon fiber and at least the one of acetylene Kind.Thus, use the conductive additive of the embodiment of the present invention, provide electron propagation ducts for anode composite, thus improve compound The electronic conductivity of positive pole, improves the chemical property of all-solid-state battery further.
According to embodiments of the invention, described negative pole, including selected from lithium sheet, graphite material, agraphitic carbon, lithium titanate, oxygen At least one of change titanium, silicon, germanium, stannum, antimony, stannum oxide, silicon oxide, ferrum oxide, cobalt oxide, nickel oxide, molybdenum oxide and copper oxide. Thus, the negative pole of the embodiment of the present invention is used, it is possible to promote the chemical property of all-solid-state battery, stability and safety.
In a third aspect of the present invention, the present invention proposes a kind of method preparing composite solid electrolyte.
According to embodiments of the invention, the method includes: by ceramic base solid electrolyte and the first polymer-based solid state electricity Solve matter to mix according to predetermined ratio, in order to obtain described composite solid electrolyte.
Inventor is it was unexpectedly observed that use the preparation method of the composite solid electrolyte of the embodiment of the present invention, this preparation side Method is easy, and process conditions are gentle, it is not necessary to complicated equipment, and manufacturing cycle is short, and its raw material sources are extensive, and the most large batch of half Continuous prodution and manufacture.It will be appreciated to those of skill in the art that above for the spy described by composite solid electrolyte Seek peace advantage, be still applied to the preparation method of this composite solid electrolyte, do not repeat them here.
It addition, preparation method according to the above embodiment of the present invention, it is also possible to have a following additional technical characteristic:
According to embodiments of the invention, the method includes: by described ceramic base solid electrolyte, the first macromolecule matrix and First lithium salts carries out the first mixing in organic media;Wherein, described organic media is the good solvent of described macromolecule matrix, bag Include at least one in acetonitrile, acetone, butanone, dimethylformamide and oxolane;And described first mixing time Between be 5~48 hours, it is preferable that 12~24 hours.
Thus, use the preparation method of composite solid electrolyte of the embodiment of the present invention, by ceramic base and polymer base Solid electrolyte is sufficiently carried out dissolving and mixing in organic media, thus obtains uniform composite solid electrolyte slurry, And further composite solid electrolyte layer after molding is finer and close and mechanical performance is higher, moreover it is possible to keep toughness.
In a fourth aspect of the present invention, the present invention proposes a kind of method preparing flexible all-solid-state battery.
According to embodiments of the invention, the method includes: composite solid electrolyte is coated in the surface of anode composite also It is dried, in order to obtain composite sheet;With attach negative pole on the surface of described composite sheet, in order to obtain described flexible all-solid-state battery; Wherein, described composite solid electrolyte is the composite solid electrolyte of any of the above-described or prepared by any of the above-described method answers Close solid electrolyte.
Inventor is it was unexpectedly observed that use the preparation method of the flexible all-solid-state battery of the embodiment of the present invention, this preparation side Method is easy, and process conditions are gentle, it is not necessary to complicated equipment, and manufacturing cycle is short, the most large batch of production and manufacture, and energy Enough prepare can at high temperature use, mechanical strength is high, security performance is good, there is the area ratio capacity of excellence and energy density, And the flexible all-solid-state battery that the internal resistance of cell is less and flexible cutting high, bent uses without impact.People in the art Member is it is understood that above for composite solid electrolyte, its preparation method and the feature described by flexible all-solid-state battery And advantage, it is still applied to the preparation method of this flexibility all-solid-state battery, does not repeats them here.
It addition, preparation method according to the above embodiment of the present invention, it is also possible to have a following additional technical characteristic:
According to embodiments of the invention, described anode composite obtains through the following steps: by positive active material, Dilithium salt, the second macromolecule matrix and conductive additive carry out the second mixing at organic media, in order to obtain anode sizing agent, to institute State anode sizing agent to be shaped, in order to obtain anode composite.
Thus, using the preparation method of the embodiment of the present invention, this preparation method is easy, and process conditions are gentle, it is not necessary to complicated Equipment, and manufacturing cycle is short, it is possible to produce macroion transporting, high electronic conductivity has with composite solid electrolyte Good interracial contact and have flexibility anode composite.
According to embodiments of the invention, described molding includes: is coated on aluminium foil by described anode sizing agent and is dried, in order to Obtain anode composite;Or described anode sizing agent is dried, dried product is suppressed on aluminium foil, in order to obtain Obtain anode composite.Inventor it was unexpectedly observed that carry out the anode composite sheet that compacting obtains after anode sizing agent after dried again, With anode sizing agent is directly coated and the similar nature of anode composite sheet of drying and moulding, and the former internal structure more causes Close.Thus, the method using the embodiment of the present invention, the anode composite prepared, its ion transporting and electronic conductivity are higher, With the interracial contact of composite solid electrolyte good more preferably, and there is more preferable flexibility.
According to embodiments of the invention, described being dried is carried out at a temperature of 20~100 degrees Celsius, it is preferable that 60 Degree Celsius;The described dry time is 5~48 hours, it is preferable that 12 hours;The composite solid electrolyte on described composite sheet surface Thickness be 10~200 microns, it is preferable that 40 microns;The time of described second mixing is 5~48 hours, it is preferable that 12~24 Hour;The pressure of described compacting is 2~20MPa, it is preferable that 4MPa;And the thickness of described anode composite is 20~1000 micro- Rice.
The present inventor finds through long-term research, prepares anode composite, composite solid electrolyte and flexibility complete During solid state battery, the numerical range of each process conditions all can affect the final performance of flexible all-solid-state battery.It is dried Time is less than 5 hours, then slurry cannot be shaped, and drying time was more than 48 hours, then the flexibility of sheet material can reduce, so being dried 12 hours most suitable;The length of incorporation time can affect the uniformity of anode composite and composite solid electrolyte, mixes too short, short In 5 hours, then mixed effect was bad, the then cost of idleness more than 48 hours, so the mixing best results of 12~24 hours;Compound The thickness of positive pole is 20~1000 microns and is advisable, and prepared by the thinnest being difficult to, and battery energy density is relatively low, blocked up then all-solid-state battery Flexibility can be greatly reduced;And the thickness of the composite solid electrolyte on composite sheet surface selects 10~200 microns, it is thinner than 10 microns Then the capacitance of all-solid-state battery is too small, is thicker than 200 microns of flexibilities affecting again all-solid-state battery, so composite solid electrolyte Thickness be 40 microns optimal.
Thus, the method using the embodiment of the present invention, this preparation method is easy, and process conditions are gentle, and manufacturing cycle is short, Be beneficial to large batch of production and manufacture, and can prepare can at high temperature use, mechanical strength is high, security performance is good, tool There are the area ratio capacity of excellence and an energy density and the internal resistance of cell is less and flexible cutting high, bent is without impact use Flexible all-solid-state battery.
In a fifth aspect of the present invention, the present invention proposes a kind of wearable electronic.According to embodiments of the invention, This wearable electronic includes above-mentioned flexible all-solid-state battery.It will be appreciated to those of skill in the art that this wearing electricity Subset can also be containing the parts of other necessity, such as integrated circuit, output device, input equipment and shell etc., at this not Repeat again.
Inventor is it was unexpectedly observed that use the wearable electronic of the embodiment of the present invention, the all-solid-state battery of this equipment Volume is little, capacitance is big and flexible, bent, cutting and do not affect the use of battery.Skilled artisans appreciate that , above for the feature and advantage described by composite solid electrolyte, flexible all-solid-state battery, it is still applied to this wearable Electronic equipment, does not repeats them here.
The additional aspect of the present invention and advantage will part be given in the following description, and part will become from the following description Obtain substantially, or recognized by the practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or the additional aspect of the present invention and advantage are from combining the accompanying drawings below description to embodiment and will become Substantially with easy to understand, wherein:
Fig. 1 is the scanning electron microscope (SEM) photograph of anode composite section according to an embodiment of the invention;
Fig. 2 is composite solid electrolyte electrochemical impedance figure at room temperature in accordance with another embodiment of the present invention;
Fig. 3 is all-solid-state battery charging and discharging curve at 60 c in accordance with another embodiment of the present invention;And
Fig. 4 is that work sheet is cut in all-solid-state battery bending in accordance with another embodiment of the present invention.
Detailed description of the invention
Embodiments of the invention are described below in detail, and those skilled in the art is it will be appreciated that example below is intended to for solving Release the present invention, and be not construed as limitation of the present invention.Unless stated otherwise, embodiment below is not expressly recited tool Body technique or condition person, those skilled in the art according to conventional technology or the condition in this area or can say according to product Bright book is carried out.Agents useful for same or instrument unreceipted production firm person, be can by city available from conventional products.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only descriptive , and limit the present invention never in any form.
Conventional method
Unless expressly stated, the test condition of following electrochemistry and the preparation method of sample are used in the examples below that:
INSTRUMENT MODEL: ZAHNER elektrik IM6 electric impedance analyzer, LAND electrochemical workstation;
The parameter of electrochemical impedance test: the amplitude range of alternating voltage is 5~50mV, the frequency model of electrochemical workstation Enclose for 0.1Hz~8MHz, or the frequency range of electric impedance analyzer is 40Hz~110MHz;
The parameter of charge-discharge performance test: voltage range 2.3V-3.8V, tests 100 microamperes/cm of electric current2;And
The preparation of electrochemical impedance sample: be vacuum dried at 60 c by electrolyte slurry 12 hours, rolls after drying Swaging becomes dielectric film, and lower surface sputters the layer gold that 200nm is thick respectively thereon, as ion blocking electrode, can pass through fixture Accommodate and test on electrochemical workstation or electric impedance analyzer.
Embodiment 1
In this embodiment, positive active material uses nickel-cobalt-manganese ternary material (LiNi0.5Co0.2Mn0.3O2), macromolecule Matrix is polyethylene glycol oxide, and lithium salts selects trifluoromethane sulfonic acid amine lithium, and conductive additive is Indium sesquioxide., and 4 kinds of raw materials are again with matter After amount mixes than 5:1:1:3 in acetonitrile, stir 12 hours under room temperature, obtain anode composite slurry.Anode composite slurry is existed It is vacuum dried 12 hours at 60 DEG C, obtains anode composite Precursor Powder, finally by anode composite Precursor Powder at the pressure of 4MPa Lower compacting, obtains the anode composite sheet that thickness is 200 microns.
The profile scanning Electronic Speculum figure of the anode composite sheet of this embodiment, as shown in Figure 1.As seen from Figure 1, employing is pressed into The anode composite sheet that type method is prepared is finer and close, does not has significantly the biggest cavity between granule, it is provided that preferably from Son and electric transmission duct, granule is held tightly together by polymer dielectric simultaneously so that anode composite sheet has soft Property.
Embodiment 2
In this embodiment, positive active material uses cobalt acid lithium, and macromolecule matrix is chlorohydrin rubber, and lithium salts selects high chlorine Acid lithium, and conductive additive is Indium sesquioxide., after 4 kinds of raw materials mix in acetone with mass ratio 2:1:1:1 again, stirs 12 under room temperature Hour, obtain anode composite slurry.Anode composite slurry is applied directly on aluminium foil, is placed at 60 DEG C vacuum drying 12 little Time, obtain the anode composite sheet that thickness is 20 microns.
Embodiment 3
In this embodiment, positive active material uses LiFePO4, and macromolecule matrix is polyethylene glycol oxide, and lithium salts selects Lithium hexafluoro phosphate, and conductive additive is electrically conductive graphite, after 4 kinds of raw materials mix in nitrile with mass ratio 36:1:1:2 again, room The lower stirring of temperature 12 hours, obtains anode composite slurry.Anode composite slurry is vacuum dried 12 hours at 60 DEG C, is combined Positive pole Precursor Powder, finally suppresses anode composite Precursor Powder under the pressure of 6MPa, and obtaining thickness is 1000 microns answer Close positive plate
Embodiment 4
In this embodiment, ceramic base solid electrolyte is Li-La-Ti oxygen, macromolecule matrix employing polyacrylonitrile, and lithium salts For lithium perchlorate, 3 kinds of raw materials mix in dimethylformamide with mass ratio 3:1:1 again, stir 24 hours, answered under room temperature Close solid electrolyte slurry.According to the sample preparation methods essentially identical with conventional method and test condition, to answering of embodiment 4 Close the electrochemical impedance sample that solid electrolyte slurry is prepared, carry out electrochemical impedance test.
For the electrochemical impedance data of the present embodiment, carry out Equivalent Circuit Fitting by software, can obtain further The all-in resistance of sample.The parameters such as the area further according to the thickness of sample and gold electrode, can finally calculate the total conductivity of sample. So, the composite solid electrolyte of the present embodiment, total ionic conductivity at room temperature is 2 × 10-4S/cm。
Embodiment 5
In this embodiment, ceramic base solid electrolyte is lithium lanthanum zirconium oxygen, macromolecule matrix employing polyethylene glycol oxide, and lithium Salt is trifluoromethane sulfonic acid amine lithium, and 3 kinds of raw materials mix in acetonitrile with mass ratio 8:1:1 again, stirs 24 hours, obtain under room temperature Composite solid electrolyte slurry.According to the sample preparation methods essentially identical with conventional method and test condition, to embodiment 5 The electrochemical impedance sample that composite solid electrolyte slurry is prepared, carries out electrochemical impedance test.
The room temperature impedance diagram of the composite solid electrolyte of this embodiment, as shown in Figure 2.As seen from Figure 2, impedance data by One semi arch and straight line composition, straight line is owing to the blocking electrode at electrolyte two ends causes, the available total electricity of matching Resistance is 510 Ω.Further, the composite solid electrolyte of this embodiment, total ionic conductivity at room temperature is 4 × 10-5S/cm。
Embodiment 6
In this embodiment, ceramic base solid electrolyte is, macromolecule matrix uses phosphoric acid germanium aluminum lithium, and lithium salts is hexafluoro Lithium phosphate, 3 kinds of raw materials mix in acetonitrile with mass ratio 4:3:3 again, stir 24 hours, obtain composite solid electrolyte under room temperature Slurry.According to the sample preparation methods essentially identical with conventional method and test condition, the composite solid electrolyte to embodiment 6 The electrochemical impedance sample that slurry is prepared, carries out electrochemical impedance test.
The composite solid electrolyte of this embodiment, total ionic conductivity at room temperature is 3 × 10-6S/cm。
Embodiment 7
In this embodiment, it is sequentially prepared out anode composite sheet, composite sheet and all-solid lithium-ion battery, then to all solid state Lithium ion battery carries out charge-discharge performance test.
(1) by iron phosphate lithium positive pole active substance, polyethylene glycol oxide, trifluoromethane sulfonic acid amine lithium, Indium sesquioxide. according to 7:1: After the mass ratio of 1:1 mixes in acetonitrile, stir 24 hours under room temperature, obtain anode composite slurry;Anode composite is starched Material is vacuum dried 24 hours at 60 DEG C, obtains anode composite Precursor Powder, then by anode composite Precursor Powder in the pressure of 4MPa It is compressed on aluminium foil under power, obtains the anode composite sheet that thickness is 300 microns;
(2) lithium lanthanum zirconium oxygen, polyethylene glycol oxide, trifluoromethane sulfonic acid amine lithium are entered in acetonitrile according to the mass ratio of 6:1:1 After row mixing, stir 24 hours under room temperature, obtain composite solid electrolyte slurry;Composite solid electrolyte slurry is printed on multiple Close the one side that positive plate does not contacts with aluminium foil;The positive plate of composite solid electrolyte will be printed with again, be placed in vacuum at 60 DEG C and do Dry 24 hours, surface must be arrived and be coated with the composite sheet that a layer thickness is 40 microns of composite solid electrolytes;
(3) lithium sheet is placed directly against on all solid state electrolyte after drying, utilizes button cell to encapsulate, obtain all solid state Battery.
The charging and discharging curve of the all-solid lithium-ion battery of this embodiment, as shown in Figure 3.As seen from Figure 3, prepare All-solid-state battery have high area ratio capacity, charge and discharge platform is obvious, and discharge capacity is put close to the theory of positive electrode material Capacitance, the coulombic efficiency of battery is close to 100%.
Further, the all-solid lithium-ion battery of this embodiment has flexibility, its bending, cutting is not affected use, tool Body is as shown in Figure 4.
Embodiment 8
In this embodiment, anode composite sheet, composite sheet and all-solid lithium-ion battery it are sequentially prepared out.
(1) by nickel-cobalt-manganese ternary material (LiNi0.5Co0.2Mn0.3O2) positive active material, polyethylene glycol oxide, perchloric acid After lithium, electrically conductive graphite mix according to the mass ratio of 7:1:1:1 in acetonitrile, stir 24 hours under room temperature, obtain anode composite slurry Material;Being printed on aluminium foil by anode composite slurry, be subsequently placed at 60 DEG C vacuum drying 24 hours, obtaining thickness is 20 microns Anode composite sheet;
(2) lithium lanthanum zirconium oxygen, polyethylene glycol oxide, lithium perchlorate are mixed, under room temperature according to the mass ratio of 8:1:1 in acetonitrile Stir 24 hours, obtain composite solid electrolyte slurry;Composite solid electrolyte slurry is printed on anode composite sheet not with aluminum The one side of paper tinsel contact;The positive plate of composite solid electrolyte slurry will be printed with again, be placed at 60 DEG C vacuum drying 24 hours, The composite sheet that a layer thickness is 40 microns of composite solid electrolytes it is coated with to surface;
(3) lithium sheet is placed directly against on all solid state electrolyte after drying, utilizes button cell to encapsulate, obtain all solid state Battery.
Sum up
Integrated embodiment 1~8 can draw, flexible all-solid lithium-ion battery proposed by the invention and preparation method thereof, This preparation method is easy, and process conditions are gentle, it is not necessary to complicated equipment, and manufacturing cycle is short, the most large batch of production and system Make, and can prepare can at high temperature use, mechanical strength is high, security performance is good, have excellence area ratio capacity and Energy density and the internal resistance of cell is less and flexible cutting high, bent uses without impact flexible all-solid-state battery.
In describing the invention, term " first ", " second " are only used for describing purpose, and it is not intended that indicate or dark Show relative importance or the implicit quantity indicating indicated technical characteristic.Thus, " first ", the feature of " second " are defined Can express or implicitly include at least one this feature.In describing the invention, " multiple " are meant that at least two, Such as two, three etc., unless otherwise expressly limited specifically.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " specifically show Example " or the description of " some examples " etc. means to combine this embodiment or example describes specific features, structure, material or spy Point is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term not Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be in office One or more embodiments or example combine in an appropriate manner.Additionally, in the case of the most conflicting, the skill of this area The feature of the different embodiments described in this specification or example and different embodiment or example can be tied by art personnel Close and combination.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is example Property, it is impossible to being interpreted as limitation of the present invention, those of ordinary skill in the art within the scope of the invention can be to above-mentioned Embodiment is changed, revises, replaces and modification.

Claims (10)

1. a composite solid electrolyte, it is characterised in that contain:
Ceramic base solid electrolyte;With
First polymer-based solid state electrolyte;
Wherein, gross weight based on described composite solid electrolyte, the content of described ceramic base solid electrolyte is 20~90 weights Amount %;
Optionally, gross weight based on described composite solid electrolyte, the content of described ceramic base solid electrolyte is 40~80 Weight %, the content of described first polymer-based solid state electrolyte is 20~60 weight %.
Composite solid electrolyte the most according to claim 1, it is characterised in that
Described ceramic base solid electrolyte includes selected from lithium lanthanum zirconium oxygen, Li-La-Ti oxygen, titanium phosphate aluminum lithium and phosphoric acid germanium aluminum lithium extremely Few one;
Described first polymer-based solid state electrolyte includes:
First lithium salts, described lithium salts includes selected from lithium perchlorate, trifluoromethane sulfonic acid amine lithium, lithium hexafluoro phosphate, LiBF4 With at least one of diacetic acid Lithium biborate;And
First macromolecule matrix, described macromolecule matrix includes selected from polyethylene glycol oxide or its modifier, poly-methyl methacrylate Ester or its modifier, Kynoar or its modifier, polyacrylonitrile or its modifier and chlorohydrin rubber or its modifier are extremely Few one.
3. a flexible all-solid-state battery, it is characterised in that be electrolysed containing the composite solid described in any one of claim 1~2 Matter.
Flexible all-solid-state battery the most according to claim 3, it is characterised in that possibly together with anode composite and negative pole;
Gross weight based on described anode composite, described anode composite includes:
Positive active material, its content is 40~90 weight %, it is preferable that 50~75 weight %,
Second polymer-based solid state electrolyte, its content is 5~40 weight %, it is preferable that 20 weight %, and
Conductive additive, its content is 5~30 weight %;
Wherein, described positive active material, including selected from cobalt acid lithium, LiMn2O4, LiFePO4 and nickel-cobalt-manganese ternary material extremely Few one;
Described second polymer-based solid state electrolyte contains:
Second lithium salts, described lithium salts includes selected from lithium perchlorate, trifluoromethane sulfonic acid amine lithium, lithium hexafluoro phosphate, LiBF4 With at least one of diacetic acid Lithium biborate;With
Second macromolecule matrix, described macromolecule matrix includes selected from polyethylene glycol oxide or its modifier, poly-methyl methacrylate Ester or its modifier, Kynoar or its modifier, polyacrylonitrile or its modifier and chlorohydrin rubber or its modifier are extremely Few one;
Described conductive additive, including selected from tin indium oxide, Indium sesquioxide., tin ash, zinc oxide, nickel oxide, ferroso-ferric oxide, At least one of conductive carbon black, electrically conductive graphite, CNT, Graphene, carbon fiber and acetylene;And
Described negative pole, including selected from lithium sheet, graphite material, agraphitic carbon, lithium titanate, titanium oxide, silicon, germanium, stannum, antimony, stannum oxide, At least one of silicon oxide, ferrum oxide, cobalt oxide, nickel oxide, molybdenum oxide and copper oxide.
5. the method for the composite solid electrolyte prepared described in any one of claim 1~2, it is characterised in that including:
Ceramic base solid electrolyte and the first polymer-based solid state electrolyte are mixed according to predetermined ratio, in order to obtain described multiple Close solid electrolyte.
Method the most according to claim 5, it is characterised in that including:
Described ceramic base solid electrolyte, the first macromolecule matrix and the first lithium salts are carried out the first mixing in organic media;
Wherein, described organic media is the good solvent of described macromolecule matrix, including selected from acetonitrile, acetone, butanone, dimethyl methyl At least one in amide and oxolane;And
The time of described first mixing is 5~48 hours, it is preferable that 12~24 hours.
7. the method for the flexible all-solid-state battery prepared described in claim 3~4, it is characterised in that including:
Composite solid electrolyte it is coated in the surface of anode composite and is dried, in order to obtaining composite sheet;With
Negative pole is attached, in order to obtain described flexible all-solid-state battery on the surface of described composite sheet;
Wherein, described composite solid electrolyte is the composite solid electrolyte described in any one of claim 1~2 or according to power Profit requires prepared by the method described in 5~6 any one.
Method the most according to claim 7, it is characterised in that described anode composite obtains through the following steps:
Positive active material, the second lithium salts, the second macromolecule matrix and conductive additive are carried out the second mixing at organic media, So that acquisition anode sizing agent, described anode sizing agent is shaped, in order to obtain anode composite;
Wherein, described molding includes:
Described anode sizing agent it is coated on aluminium foil and is dried, in order to obtaining anode composite;Or
Described anode sizing agent is dried, dried product is suppressed on aluminium foil, in order to obtain anode composite.
9. according to the method described in claim 7 and 8, it is characterised in that
Described being dried is carried out at a temperature of 20~100 degrees Celsius, it is preferable that 60 degrees Celsius;
The described dry time is 5~48 hours, it is preferable that 12 hours;
The thickness of the composite solid electrolyte on described composite sheet surface is 10~200 microns, it is preferable that 40 microns;
The time of described second mixing is 5~48 hours, it is preferable that 12~24 hours;
The pressure of described compacting is 2~20MPa, it is preferable that 4MPa;And
The thickness of described anode composite is 20~1000 microns.
10. a wearable electronic, it is characterised in that include the flexible all-solid-state battery described in claim 3~4.
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