CN105811002A - Organic and inorganic composite all-solid-state electrolyte and all-solid-state battery formed from same - Google Patents

Organic and inorganic composite all-solid-state electrolyte and all-solid-state battery formed from same Download PDF

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Publication number
CN105811002A
CN105811002A CN201610148922.6A CN201610148922A CN105811002A CN 105811002 A CN105811002 A CN 105811002A CN 201610148922 A CN201610148922 A CN 201610148922A CN 105811002 A CN105811002 A CN 105811002A
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lithium
solid state
organo
state electrolyte
electrolyte
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崔光磊
张建军
温慧婕
李阳
徐红霞
刘志宏
高继超
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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 invention relates to an organic and inorganic composite all-solid-state electrolyte, in particular to an organic polycarbonate macromolecule and inorganic fast-ion conductor composite all-solid-state electrode and preparation and application of an all-solid-state battery formed from the same. The organic and inorganic composite all-solid-state electrolyte comprises polycarbonate macromolecule, an inorganic fast-ion conductor, a lithium salt and a porous rigid support material, the thickness of the organic and inorganic composite all-solid-state electrolyte is 5-2,000 micrometers, the mechanical strength is 2-150MPa, the room-temperature ionic conductivity is 1*10<-4>-6*10<-3> S/cm, and an electrochemical window is greater than 4V. The organic and inorganic composite all-solid-state electrolyte provided by the invention is easy to prepare and simple to form, has favorable mechanical property, and is relatively high in room-temperature ionic conductivity and relatively wide in electrochemical window; and meanwhile, by the organic and inorganic composite all-solid-state electrolyte, the growth of lithium dendrites of a negative electrode can be effectively prevented, the interface stability is improved, and the long-circulation and safe application performance of the battery are further improved.

Description

A kind of organo-mineral complexing all solid state electrolyte and the solid lithium battery of composition thereof
Technical field
The present invention relates to solid electrolyte, a kind of organo-mineral complexing all solid state electrolyte and composition thereof The preparation of all solid state serondary lithium battery and application.
Background technology
In recent years, along with the development of electric automobile, electrical network energy storage etc., people are to high security, the power of high-energy-density The demand of battery and energy-storage system is more and more urgent.In business-like electrochemical energy storage device, lithium ion battery is undoubtedly Good selection.At present, the electrolyte that business-like lithium ion battery uses mainly has two kinds: one is liquid electrolyte, another Planting is gel electrolyte.Liquid electrolyte by lithium salts (such as LiPF6, LiTFSI and LiBF4Deng), organic solvent is (such as cyclic carbonate Ester, linear carbonate, carboxylic acid esters etc.) and several functions additive composition.Gel electrolyte is the polymeric matrix of porous Middle absorption electrolyte forms gel.Identical with liquid electrolyte, the electrolyte in gel electrolyte plays ionic conduction and negative Surface, pole forms the effect of stable solid electrolyte film (SEI).Above two electrolyte has higher ionic conductivity, energy Enough electrodes that effectively infiltrates, and stable solid electrolyte film, the most existing commercial li-ion electricity can be formed at electrode surface Pond has the relatively low internal resistance of cell and good cyclical stability.But, liquid electrolyte and gel electrolyte all contain in a large number Organic solvent inflammable, volatile.When inside battery due to high current charge-discharge or short circuit and temperature raise time, electrolyte with electricity Chemical reaction between pole will be accelerated rapidly, and then causes thermal runaway.This process produces with a large amount of gases, ultimately results in Cell sealing lost efficacy and catching fire blast.In recent years, the security incident of high capacity lithium ion battery happens occasionally.Although passing through Add fire retardant, use refractory ceramics barrier film, positive and negative pole material surface modify, optimize battery structure Design and optimization BMS, Battery core outer surface phase transformation fire proofing, improve the measures such as cooling system, existing lithium-ion electric can be improved to a great extent The safety in pond, but these measures cannot be inherently eliminated the potential safety hazard of high capacity cell system, particularly at battery pole Under the conditions of end uses, when there is safety issue in local cell unit.
In order to solve existing commercial liquid lithium ion battery problem encountered, it is solid that scientific research personnel is greatly developing use The lithium ion battery of body electrolyte, has an advantage in that:
1) solid electrolyte is non-volatile, the most non-combustible, therefore uses solid, excellent in safety；
2) solid electrolytic mass-energy keeps stable within the scope of wide temperature, and Applicable temperature scope is wide, particularly under high temperature；
3) some solid electrolytic confrontation moisture are insensitive, it is possible to keep good chemical stability the most for a long time, it is easy to Preparation；
4) solid electrolyte material has wider electrochemical window, and this makes high-voltage electrode material be expected to be applied, from And improve battery energy density；
5) solid electrolyte is fine and close, and has higher intensity and hardness, it is possible to effectively stoping piercing through of Li dendrite, this makes Lithium metal is used as negative pole and is possibly realized.
In sum, considering from basic specificity analysis, if searching out suitable material system, using solid electrolyte Solid lithium battery, can have excellence security feature, cycle characteristics, high energy density and low cost.
Solid electrolyte is broadly divided into copolymer solid electrolyte, inorganic solid electrolyte.Copolymer solid electrolyte It it is the electrolyte using lithium salts to be compounded to form with polymer.It has higher conductance more than glass transition temperature Rate, and there is good pliability and tensile and shear property, it is easy to it is prepared as flexible bendable battery.At polymer solid electrolyte In matter, by interacting with macromolecule, lithium salts can occur a certain degree of negative ions to dissociate, with high molecular polar group Group's complexation forms coordination compound.During polymer segment is wriggled, negative ions constantly dissociates with original group, and with neighbouring Group complexation, under the effect of extra electric field, it is possible to achieve the displacement of ion, thus realizes the conduction of negative ions.Specially Profit CN101440177A discloses a kind of preparation of polymer solid electrolyte, and the method uses epoxy resin and butyronitrile rubber Glue is blended the matrix as solid electrolyte, matrix is dissolved in together with lithium perchlorate oxolane, then uses solution casting method Preparing composite polymer solid electrolyte, prepared copolymer solid electrolyte is 20oIonic conductivity maximum under C is 9 ×10-5 S cm-1.CN201410683144.1 discloses a kind of poly(ethylene oxide) base full solid state polymer electrolyte, its room temperature Electrical conductivity is 10-5 S cm-1.Polymer dielectric, conductivity at room temperature is on the low side, it is difficult to meet answering of room temperature lithium ion battery With.Relative to copolymer solid electrolyte, inorganic solid electrolyte can keep chemical stability within the scope of wide temperature, electricity Chemistry window width, mechanical strength is higher, and therefore battery based on inorganic solid electrolyte has higher security feature. CN103594726A discloses garnet structure tantalic acid lanthanum lithio solid electrolyte material and preparation method thereof, this electrolyte Electrical conductivity when room temperature is 6 × 10 to the maximum-4 S cm-1.Application for a patent for invention description CN201410710254.2 discloses A kind of anti-perovskite sulfide solid electrolyte, 20oUnder C, ionic conductivity is 10-3 S cm-1.Although room-temperature ion conductance Rate is higher, but inorganic solid electrolyte fragility is relatively big, and pliability is poor, complicated process of preparation, relatively costly.Organo-mineral complexing is complete Solid electrolyte, by solid polymer electrolyte is combined with inorganic solid electrolyte, the advantage that can be taken into account the two, processing Molding is easy, and ionic conductivity height, electrochemical stability height etc. are many a little, farthest realize the comprehensive of solid electrolyte The lifting of performance.
Summary of the invention
The technical solution used in the present invention is for achieving the above object:
A kind of organo-mineral complexing all solid state electrolyte, its by Merlon family macromolecule, lithium salts, porous rigid backing material, And inorganic fast ionic conductor composition；Its thickness is 5 μm-2000 μm；Mechanical strength is 2 MPa-150 MPa, room temperature from Electron conductivity is 1 × 10-4 S/cm-6×10-3 S/cm, electrochemical window is more than 4 V.
Described Merlon family macromolecule has a structure as shown in formula 1:
Formula 1
Wherein, the value of a is 1-50000, and the value of b is 1-50000.
R1For:
,Or
R2For:
,Or
In above-mentioned substituent group, X is fluorine, phenyl, hydroxyl or Sulfonic Lithium；Wherein the value of m1 is 0-2, and the value of n1 is 0-2, and m1 It is 0 time different from n1；The value of m2 is 0-2, and the value of n2 is 0-2, and is 0 when m2 from n2 is different；The value of m3 is 0-2, n3 Value be 0-2, and be 0 when m3 from n3 is different；Merlon family macromolecule is in organo-mineral complexing all solid state electrolyte Mass fraction is 3 %-85 %；
Described inorganic fast ionic conductor is Li7La3Zr2O12、Li10GeP2S12、Li3OCl0.5Br0.5、Li3xLa(2/3)-xTiO3 (0.04 < x < 0.14), Li5La3M2O12(M=Ta, Nb), Li5.5La3Nb1.75In0.25O12、Li3N-LiX(X=Cl, Br, I), Li14Zn(GeO4)4、LiZr2(PO4)3、Li3OCl、LiPON、Li2S-MaSb(M=Al, Si, P；Wherein the value of a and b is 1-3) One or several, inorganic fast ionic conductor mass fraction in organo-mineral complexing all solid state electrolyte is 1 %-50 %；
Described lithium salts is lithium perchlorate, lithium hexafluoro phosphate, dioxalic acid Lithium biborate, hexafluoroarsenate lithium, LiBF4, trifluoromethyl Sulfonic Lithium, double fluoromethane sulfimide lithium one or several；Lithium salts matter in organo-mineral complexing all solid state electrolyte Amount mark is 3 %-42 %；
Described porous rigid backing material is cellulose non-woven film, alginate fibre nonwoven film；Aramid fiber nonwoven film；Aromatic polysulfonamide without Spin film；Polypropylene non-woven film；One in glass fibre, pet film, polyimides nonwoven film is many Rigid backing material mass fraction in organo-mineral complexing all solid state electrolyte in hole is 5 %-30 %.
Preferably technical scheme is:
Merlon family macromolecule is poly (propylene carbonate) or polyethylencarbonate；Merlon family macromolecule is at organic and inorganic compound The addition closed in all solid state electrolyte is 30 %-75 %；
Inorganic fast ionic conductor is Li7La3Zr2O12、Li10GeP2S12；Inorganic fast ionic conductor is all solid state at organo-mineral complexing Addition in electrolyte is 5 %-30 %；
Lithium salts is lithium perchlorate or double fluoromethane sulfimide lithium；Lithium salts interpolation in organo-mineral complexing total solids electrolyte Amount is 5 %-20 %；
Porous rigid backing material is cellulose non-woven film or polyimides nonwoven film, and porous rigid backing material is at organic-inorganic Mass fraction in compound all solid state electrolyte is 10 %-25 %.
Preferred technical scheme is:
Merlon family macromolecule is poly (propylene carbonate)；Merlon family macromolecule is at organo-mineral complexing all solid state electrolyte In addition be 40 %-65 %；
Inorganic fast ionic conductor is Li7La3Zr2O12；Inorganic fast ionic conductor adding in organo-mineral complexing all solid state electrolyte Dosage is 8 %-20 %；
Lithium salts is double fluoromethane sulfimide lithium；Lithium salts addition in organo-mineral complexing all solid state electrolyte is 10 %- 15 %；
Solvent is N,N-dimethylformamide；
Porous rigid backing material is cellulose non-woven film, and porous rigid backing material is at organo-mineral complexing all solid state electrolyte In mass fraction be 15 %-25 %.
A kind of preparation method of organo-mineral complexing all solid state electrolyte:
1) Merlon family macromolecule and lithium salts being dissolved in solvent, stirring, to being completely dissolved, obtains homogeneous polycarbonate-based Macromolecule/lithium salt solution；
2) in above-mentioned homogeneous solution, add inorganic fast ionic conductor, continue stirring after addition to mix homogeneously；
3) by the solution of above-mentioned mix homogeneously masking on porous rigid backing material, vacuum drying, obtain organo-mineral complexing All solid state electrolyte.
Described Merlon family macromolecule has a structure as shown in formula 1:
Formula 1
Wherein, the value of a is 1-50000, and the value of b is 1-50000.
R1For:
,Or
R2For:
,Or
In above-mentioned substituent group, X is fluorine, phenyl, hydroxyl or Sulfonic Lithium.Wherein the value of m1 is 0-2, and the value of n1 is 0-2；M2's Value is 0-2, and the value of n2 is 0-2；The value of m3 is 0-2, and the value of n3 is 0-2；Merlon family macromolecule is in organic nothing The mass fraction that machine is combined in all solid state electrolyte is 3 %-85 %；
Described inorganic fast ionic conductor is Li7La3Zr2O12、Li10GeP2S12、Li3OCl0.5Br0.5、Li3xLa(2/3)-xTiO3 (0.04 < x < 0.14), Li5La3M2O12(M=Ta, Nb), Li5.5La3Nb1.75In0.25O12、Li3N-LiX(X=Cl, Br, I), Li14Zn(GeO4)4、LiZr2(PO4)3、Li3OCl、LiPON、Li2S-MaSb(M=Al, Si, P；Wherein the value of a and b is 1-3) One or several, inorganic fast ionic conductor mass fraction in organo-mineral complexing all solid state electrolyte is 1 %-50 %；
Described lithium salts is lithium perchlorate, lithium hexafluoro phosphate, dioxalic acid Lithium biborate, hexafluoroarsenate lithium, LiBF4, trifluoromethyl Sulfonic Lithium, double fluoromethane sulfimide lithium one or several；Lithium salts matter in organo-mineral complexing all solid state electrolyte Amount mark is 3 %-42 %；
Described porous rigid backing material is cellulose non-woven film, alginate fibre nonwoven film；Aramid fiber nonwoven film；Aromatic polysulfonamide without Spin film；Polypropylene non-woven film；One in glass fibre, pet film, polyimides nonwoven film is many Rigid backing material mass fraction in organo-mineral complexing all solid state electrolyte in hole is 5 %-30 %；
Described solvent be acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, sulfurous acid diethyl ester, acetone, oxolane, One among chloroform, ethyl acetate, N-Methyl pyrrolidone, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide Or it is several.
Preferably technical scheme is:
Merlon family macromolecule is poly (propylene carbonate) or polyethylencarbonate；Merlon family macromolecule is at organic and inorganic compound The addition closed in all solid state electrolyte is 30 %-75 %；
Inorganic fast ionic conductor is Li7La3Zr2O12、Li10GeP2S12；Inorganic fast ionic conductor is all solid state at organo-mineral complexing Addition in electrolyte is 5 %-30 %；
Lithium salts is lithium perchlorate or double fluoromethane sulfimide lithium；Lithium salts interpolation in organo-mineral complexing total solids electrolyte Amount is 5 %-20 %；
Porous rigid backing material is cellulose non-woven film or polyimides nonwoven film, and porous rigid backing material is at organic-inorganic Mass fraction in compound all solid state electrolyte is 10 %-25 %.
Preferred technical scheme is:
Merlon family macromolecule is poly (propylene carbonate)；Merlon family macromolecule is at organo-mineral complexing all solid state electrolyte In addition be 40 %-65 %；
Inorganic fast ionic conductor is Li7La3Zr2O12；Inorganic fast ionic conductor adding in organo-mineral complexing all solid state electrolyte Dosage is 8 %-20 %；
Lithium salts is double fluoromethane sulfimide lithium；Lithium salts addition in organo-mineral complexing all solid state electrolyte is 10 %- 15 %；
Solvent is N,N-dimethylformamide；
Porous rigid backing material is cellulose non-woven film, and porous rigid backing material is at organo-mineral complexing all solid state electrolyte In mass fraction be 15 %-25 %.
The application of a kind of organo-mineral complexing all solid state electrolyte, described electrolyte is used for preparing solid lithium battery.
Further, described organo-mineral complexing all solid state electrolyte is preparing all solid lithium metal battery, all solid state Application in lithium ion battery or all solid state lithium-sulfur cell.
A kind of all solid state serondary lithium battery, including positive pole, negative pole, the electrolyte between both positive and negative polarity, described electrolyte For organo-mineral complexing all solid state electrolyte；
The active material of described positive pole be cobalt acid lithium, LiFePO4, iron manganese phosphate for lithium, LiMn2O4, nickel ion doped, lithium-rich manganese-based, Ternary material, sulfur, sulfur compound, iron sulfate lithium, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium ferrum fluorophosphate, lithium manganese oxygen One or more in compound, conducting polymer；
The active material of negative pole be lithium metal, lithium metal alloy, graphite, hard carbon, molybdenum bisuphide, lithium titanate, carbon-silicon composite material, Carbon germanium composite, carbon tin composite material, stibium oxide, antimony carbon composite, stannum antimony composite, Li-Ti oxide, lithium metal One or more in nitride.
Wherein, it is adaptable to the most extremely sulfur of all solid state secondary lithium-sulfur cell and sulfur compound, negative pole is lithium metal and metal Lithium alloy.
The preparation of a kind of all solid state serondary lithium battery, separates both positive and negative polarity pole piece with above-mentioned electrolyte, seals entirely solid State serondary lithium battery.
Advantage for present invention:
Organo-mineral complexing all solid state electrolyte in the present invention be by polycarbonate-based solid polymer electrolyte with inorganic soon Ion conductor is composited.It had both had good pliability and the tensile shear of polycarbonate-based solid polymer electrolyte Can, inherit again inorganic fast ionic conductor chemical stability good, electrochemical window width, the plurality of advantages such as mechanical strength is high, comprehensively Excellent performance.
Easily, molding is simple, and mechanical strength is 2 MPa in the organo-mineral complexing total solids electrolyte preparation that the present invention obtains -150 MPa, conductivity at room temperature is 1 × 10-4 S/cm -6×10-3 S/cm, electrochemical window is more than 4 V.Meanwhile This solid electrolyte effectively suppresses the growth of negative pole Li dendrite, improves interface stability performance and long circulating performance.And this Not using inflammable and explosive organic solvent in bright electrolyte, eliminate this potential safety hazard, the safety being greatly improved lithium battery makes Use performance.May be used on solid lithium battery (including lithium-sulfur cell), all-solid lithium-ion battery and other secondary high-energy lithiums In battery.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of all solid state polyeletrolyte of organo-mineral complexing that the embodiment of the present invention 1 provides.
Fig. 2 is that the LiFePO4/lithium battery using the organo-mineral complexing all solid state electrolyte of embodiment 1 to assemble is in room temperature Time 1 C charging and discharging curve.
Fig. 3 is the long circulating after using the organo-mineral complexing all solid state electrolyte of embodiment 2 preparation to assemble lithium-sulfur cell Curve chart.
Detailed description of the invention
The present invention is to solve that existing electrochemical energy storage lithium-ion battery systems uses liquid electrolyte, easily reveal, perishable The problem losing, having potential safety hazard, or the problem of the poor and difficult molding of mechanical performance of gel electrolyte itself.The present invention carries Supply a kind of organo-mineral complexing all solid state electrolyte, improve the safe application performance of existing battery.
Embodiment 1
2 g poly (propylene carbonate)s, 18 g N,N-dimethylacetamide are joined in the reagent bottle of 100 ml, then at room temperature Lower stirring 6 h, obtains homogeneous poly (propylene carbonate) solution.Then by 0.2 g dioxalic acid Lithium biborate and 0.25 g Li7La3Zr2O12Joining in the middle of above-mentioned homogeneous solution, stirring 1 day, gets a uniform mixture at normal temperatures.Solution is equal Even be poured on cellulosic nonwoven fabric, be dried 1 day under the conditions of 60 DEG C of vacuum drying ovens, be dried, obtain poly (propylene carbonate)- Li7La3Zr2O12Organo-mineral complexing all solid state electrolyte.
Embodiment 2
2 g poly (propylene carbonate)s, 16 g oxolanes are joined in the reagent bottle of 100 ml, stir 6 h the most at normal temperatures, Obtain homogeneous poly (propylene carbonate) solution.Then by double for 0.2 g fluoromethane sulfimide lithium and 0.2 g Li10GeP2S12Add In the middle of above-mentioned homogeneous solution, stir 12 h at normal temperatures, get a uniform mixture.Solution is uniformly poured into glass fibers In dimension, it is dried 1 day under the conditions of 100 DEG C of vacuum drying ovens, is dried, obtains poly (propylene carbonate)-Li10GeP2S12Organic and inorganic compound Close all solid state electrolyte.
Embodiment 3
4 g polyethylencarbonate, 36 g DMFs are joined in the reagent bottle of 250 ml, then at room temperature Lower stirring 8 h, obtains homogeneous polyethylencarbonate solution.Then by 0.4 g lithium perchlorate and 0.5g Li10GeP2S12Add In the middle of above-mentioned homogeneous solution, stir 15 h at normal temperatures, get a uniform mixture.Solution is uniformly poured into a mould polyimides On nonwoven film, it is dried 1 day under the conditions of 60 DEG C of vacuum drying ovens, is dried, obtains polyethylencarbonate-Li10GeP2S12Organic-inorganic Compound all solid state electrolyte.
Embodiment 4
3 g polymerized thylene carbonate butyl esters, 20 g acetone are joined in the reagent bottle of 100 ml, stir 6 h the most at normal temperatures, To homogeneous polymerized thylene carbonate butyl acetate solution.Then by 0.6 g lithium hexafluoro phosphate and 0.4 g Li7La3Zr2O12Join above-mentioned all In the middle of the solution of one, stir 15 h at normal temperatures, get a uniform mixture.Solution is uniformly poured into aromatic polysulfonamide nonwoven On film, it is dried 1 day under the conditions of 80 DEG C of vacuum drying ovens, is dried, obtains polymerized thylene carbonate butyl ester-Li7La3Zr2O12Organic and inorganic compound Close all solid state electrolyte.
Embodiment 5
4 g polyethylencarbonate, 36 g acetonitriles are joined in the reagent bottle of 250 ml, stir 8 h the most at normal temperatures, To homogeneous polyethylencarbonate solution.Then 0.8 g LiBF4 and 0.6 g LiPON are joined above-mentioned homogeneous molten In the middle of liquid, stir 5 h at normal temperatures, get a uniform mixture.Solution is uniformly poured on aramid fiber nonwoven film, at 80 DEG C It is dried 1 day under the conditions of vacuum drying oven, is dried, obtains polyethylencarbonate-LiPON organo-mineral complexing all solid state electrolyte.
Embodiment 6
3 g polymerized thylene carbonate butyl esters, 24 g acetone are joined in the reagent bottle of 100 ml, stir 7 h the most at normal temperatures, To homogeneous polymerized thylene carbonate butyl acetate solution.Then by 0.5 g dioxalic acid Lithium biborate and 0.7 g LiZr2(PO4) join above-mentioned In the middle of homogeneous solution, stirring 1 day, gets a uniform mixture at normal temperatures.Solution is uniformly poured into alginate fibre nonwoven On film, it is dried 1 day under the conditions of 40 DEG C of vacuum drying ovens, is dried, obtains polyethylencarbonate-LiZr2(PO4) organic and inorganic compound Close all solid state electrolyte.
Electrolyte performance characterizes:
Film thickness: use the thickness of micrometer (precision 0.01 millimeter) test organo-mineral complexing all solid state electrolyte, arbitrarily take 5 points on sample, and average.
Ionic conductivity: clamp electrolyte with two panels rustless steel, is placed in 2032 type battery cases.Sodium ion electrical conductivity uses Electrochemical alternate impedance spectrum is measured, and uses formula: σ=L/ARb, wherein, L is the thickness of electrolyte, and A is stainless steel substrates room Temperature area, RbThe impedance drawn for measurement.
Electrochemical window: clamp electrolyte with stainless steel substrates and sodium sheet, is placed in 2032 type battery cases.Electrochemical window with Electrochemical workstation carries out linear voltammetric scan measurement, and take-off potential is 2.5 V, and maximum potential is 5.5 V, and scanning speed is 1 mV/s.(seeing table 1).
Acquired results is listed in table 1.From the results shown in Table 1, the organo-mineral complexing using the present invention to provide is entirely solid The mechanical strength of state electrolyte is taller and bigger in 2 Mpa；Room temperature ionic conductivity range is 1 × 10-5 S/cm-6×10-3 S/ Cm, can be with high rate charge-discharge；Electrochemical window is more than 4 V, can carry out discharge and recharge at higher voltages, and then promote energy Metric density.
Test battery performance comprises the following steps:
(1) preparation of positive plate
Kynoar (PVdF) is dissolved in N, N-2-methyl pyrrolidone by A, and concentration is 0.1 mol/L.
After PVdF, positive electrode active materials, conductive black are mixed by B with the mass ratio of 10:80:10, grind at least 1 hour.
The slurry of upper step gained is evenly coated on aluminium foil by C, and thickness is 100-120 μm, first dries at 60 DEG C, Dry under 120 DEG C of vacuum drying ovens, roll-in, punching, continue after weighing to dry in 120 DEG C of vacuum drying ovens, be put in glove In case standby.
D presses size cutting.
(2) preparation of negative plate
PVdF is dissolved in N, N-2-methyl pyrrolidone by A, and concentration is 0.1 mol/L.
After PVdF, negative active core-shell material, conductive black are mixed by B with the mass ratio of 10:80:10, grind at least 1 hour.
The slurry of upper step gained is evenly coated on Copper Foil by C, and thickness is 100-120 μm, first dries at 60 DEG C, Dry under 120 DEG C of vacuum drying ovens, roll-in, punching, continue after weighing to dry in 120 DEG C of vacuum drying ovens, be put in glove In case standby.
D presses size cutting.
(3) battery assembles
(4) battery charging/discharging performance testing
Test mode is as follows: test charging and discharging curve and the long circulating of all solid state serondary lithium battery with LAND battery charge and discharge instrument Energy.(seeing Fig. 2 and Fig. 3).
As seen from Figure 2: using LiFePO4/lithium metal battery that organo-mineral complexing all solid state electrolyte assembles, it is put Electricity specific capacity can reach 120 mAh g-1, charging and discharging curve is more steady.
As seen from Figure 3: use the length of the LiFePO4/lithium metal battery of organo-mineral complexing all solid state electrolyte assembling to follow Ring Performance comparision is stable.
Table 1

Claims (8)

1. an organo-mineral complexing all solid state electrolyte, it is characterised in that: this organo-mineral complexing all solid state electrolyte is by gathering Carbonates macromolecule, inorganic fast ionic conductor, lithium salts and porous rigid backing material are constituted；Its thickness be 5 μm- 2000 μm；Mechanical strength is 2 MPa-150 MPa, and conductivity at room temperature is 1 × 10-4 S/cm - 6×10-3 S/cm, electricity Chemistry window is more than 4 V.
2. the organo-mineral complexing all solid state electrolyte as described in claim 1, it is characterised in that:
Described Merlon family macromolecule has a structure as shown in formula 1:
Formula 1
Wherein, the value of a is 1-50000, and the value of b is 1-50000；
R1For:
,Or,
R2For:
,Or,
In above-mentioned substituent group, X is fluorine, phenyl, hydroxyl or Sulfonic Lithium；Wherein the value of m1 is 0-2, and the value of n1 is 0-2, and m1 It is 0 time different from n1；The value of m2 is 0-2, and the value of n2 is 0-2, and is 0 when m2 from n2 is different；The value of m3 is 0-2, n3 Value be 0-2, and be 0 when m3 from n3 is different；Merlon family macromolecule is in organo-mineral complexing all solid state electrolyte Mass fraction is 3 %-85 %；
Described inorganic fast ionic conductor is Li7La3Zr2O12、Li10GeP2S12、Li3OCl0.5Br0.5、Li3xLa(2/3)-xTiO3 (0.04 < x < 0.14), Li5La3M2O12(M=Ta, Nb), Li5.5La3Nb1.75In0.25O12、Li3N-LiX(X=Cl, Br, I), Li14Zn(GeO4)4、LiZr2(PO4)3、Li3OCl、LiPON、Li2S-MaSb(M=Al, Si, P；Wherein the value of a and b is 1-3) One or several, inorganic fast ionic conductor mass fraction in organo-mineral complexing all solid state electrolyte is 1 %-50 %；
Described lithium salts is lithium perchlorate, lithium hexafluoro phosphate, dioxalic acid Lithium biborate, hexafluoroarsenate lithium, LiBF4, trifluoromethyl Sulfonic Lithium, double fluoromethane sulfimide lithium one or several；Lithium salts matter in organo-mineral complexing all solid state electrolyte Amount mark is 3 %-42 %；
Described porous rigid backing material is cellulose non-woven film, alginate fibre nonwoven film；Aramid fiber nonwoven film；Aromatic polysulfonamide without Spin film；Polypropylene non-woven film；One in glass fibre, pet film, polyimides nonwoven film is many Rigid backing material mass fraction in organo-mineral complexing all solid state electrolyte in hole is 5 %-30 %.
3. the preparation method of the organo-mineral complexing all solid state electrolyte described in a claim 1, it is characterised in that:
1) Merlon family macromolecule and lithium salts being dissolved in solvent, stirring, to being completely dissolved, obtains homogeneous polycarbonate-based Macromolecule/lithium salt solution；
2) in above-mentioned homogeneous solution, add inorganic fast ionic conductor, continue stirring after addition to mix homogeneously；
3) by the solution of above-mentioned mix homogeneously masking on porous rigid backing material, vacuum drying, obtain organo-mineral complexing All solid state electrolyte.
4. the preparation method of a kind of organo-mineral complexing all solid state electrolyte as described in claim 3, it is characterised in that:
Described Merlon family macromolecule has a structure as shown in formula 1:
Formula 1
Wherein, the value of a is 1-50000, and the value of b is 1-50000；
R1For:
,Or
R2For:
,Or
In above-mentioned substituent group, X is fluorine, phenyl, hydroxyl or Sulfonic Lithium；Wherein the value of m1 is 0-2, and the value of n1 is 0-2, and m1 It is 0 time different from n1；The value of m2 is 0-2, and the value of n2 is 0-2, and is 0 when m2 from n2 is different；The value of m3 is 0-2, n3 Value be 0-2, and be 0 when m3 from n3 is different；Merlon family macromolecule is in organo-mineral complexing all solid state electrolyte Mass fraction is 3 %-85%；
Described inorganic fast ionic conductor is Li7La3Zr2O12、Li10GeP2S12、Li3OCl0.5Br0.5、Li3xLa(2/3)-xTiO3 (0.04 < x < 0.14), Li5La3M2O12(M=Ta, Nb), Li5.5La3Nb1.75In0.25O12、Li3N-LiX(X=Cl, Br, I), Li14Zn(GeO4)4、LiZr2(PO4)3、Li3OCl、LiPON、Li2S-MaSb(M=Al, Si, P；Wherein the value of a and b is 1-3) One or several, inorganic fast ionic conductor mass fraction in organo-mineral complexing all solid state electrolyte is 1 %-50 %；
Described lithium salts is lithium perchlorate, lithium hexafluoro phosphate, dioxalic acid Lithium biborate, hexafluoroarsenate lithium, LiBF4, trifluoromethyl Sulfonic Lithium, double fluoromethane sulfimide lithium one or several；Lithium salts matter in organo-mineral complexing all solid state electrolyte Amount mark is 3 %-42 %；
Described porous rigid backing material is cellulose non-woven film, alginate fibre nonwoven film；Aramid fiber nonwoven film；Aromatic polysulfonamide without Spin film；Polypropylene non-woven film；One in glass fibre, pet film, polyimides nonwoven film is many Rigid backing material mass fraction in organo-mineral complexing all solid state electrolyte in hole is 5 %-30 %.
5. the preparation method of the organo-mineral complexing all solid state electrolyte as described in claim 3, it is characterised in that: described solvent For acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, sulfurous acid diethyl ester, acetone, oxolane, chloroform, second One or more in acetoacetic ester, N-Methyl pyrrolidone, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide.
6. the application in all solid state serondary lithium battery of the organo-mineral complexing all solid state electrolyte described in a claim 1.
7. an all solid state serondary lithium battery, including positive pole, negative pole, the electrolyte between both positive and negative polarity, it is characterised in that: institute Stating electrolyte is the organo-mineral complexing full solid state polymer electrolyte described in claim 1；The active material of described positive pole is Cobalt acid lithium, LiFePO4, iron manganese phosphate for lithium, LiMn2O4, nickel ion doped, lithium-rich manganese-based, ternary material, sulfur, sulfur compound, sulphuric acid One in ferrum lithium, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium ferrum fluorophosphate, lithium manganese oxide, conducting polymer or Several；
The active material of negative pole be lithium metal, lithium metal alloy, graphite, hard carbon, molybdenum bisuphide, lithium titanate, carbon-silicon composite material, Carbon germanium composite, carbon tin composite material, stibium oxide, antimony carbon composite, stannum antimony composite, Li-Ti oxide, lithium metal One or more in nitride.
8. the preparation of an all solid state serondary lithium battery, it is characterised in that: entirely solid with the organo-mineral complexing described in claim 1 Both positive and negative polarity pole piece is separated by state electrolyte, seals to obtain all solid state serondary lithium battery.
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