CN106328992A - Lithium ion battery and preparation method thereof - Google Patents

Lithium ion battery and preparation method thereof Download PDF

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CN106328992A
CN106328992A CN201510371599.4A CN201510371599A CN106328992A CN 106328992 A CN106328992 A CN 106328992A CN 201510371599 A CN201510371599 A CN 201510371599A CN 106328992 A CN106328992 A CN 106328992A
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solid
electrolyte layer
state
lithium ion
electrolyte
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CN106328992B (en
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马永军
易观贵
王向慧
谢静
郭姿珠
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BYD Co Ltd
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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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a lithium ion battery and a preparation method thereof. The lithium ion battery comprises a battery shell body and an electrical core located in the battery shell body; the electrical core includes a positive electrode, a negative electrode and an electrolyte located between the positive electrode and the negative electrode; the electrolyte is characterized in that the electrolyte comprises a first solid electrolyte layer located on the positive electrode surface and a second solid electrolyte layer located on the negative electrode surface, and the first solid electrolyte layer makes contact with the second solid electrolyte layer; the first solid electrolyte layer comprises a first binder and first inorganic electrolyte particles, the first inorganic electrolyte particles are an NASICON type inorganic electrolyte and/or a perovskite type inorganic electrolyte; the second solid electrolyte layer comprises a second binder and second inorganic electrolyte particles, and the second inorganic electrolyte particles are an sulfide based solid electrolyte. The lithium ion battery prepared by the method has the advantages of high safety, relatively high capacity and good cycle performance.

Description

A kind of lithium ion battery and the preparation method of this lithium ion battery
Technical field
The invention belongs to field of lithium ion battery, particularly relate to a kind of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is compared with other batteries, have light weight, volume is little, running voltage is high, energy density is high, output is big, charge efficiency is high, memory-less effect, the advantage such as have extended cycle life, not only it is widely used in the field such as mobile phone, notebook computer, and one of it is also considered as the optimum selection of electric motor car, large-scale energy storage device, the current widely used liquid electrolyte of commercial li-ion battery；But, there is volatility and combustibility in organic liquid electrolyte, causing lithium ion battery to there is leakage, the risk burnt, explode, owing to organic liquid electrolyte exists volatility and combustibility, the lithium ion battery of electrolyte system cannot be completely eliminated potential safety hazard always.On the other hand, owing to electrolyte existing small molecule solvent, there is the problem that solvent oxidation is decomposed when cathode voltage is too high, thus high pressure, high-energy-density positive electrode slowly cannot popularization and application, the energy density of battery is difficult to improve further；Particularly current energy storage and electric automobiles are higher to the requirement of lithium battery safety, and the safety problem thoroughly solving lithium battery seems extremely urgent.The ultimate strategy eliminating lithium battery security risk is to use solid electrolyte to replace electrolyte to prepare all-solid-state battery.
Solid lithium battery is divided into all solid-state thin-film lithium battery and accumulation type (bulk-type) solid lithium battery.All solid-state thin-film lithium battery is to use gas-phase deposition to prepare positive pole, electrolyte, negative pole respectively, and whole process needs to realize molecular level deposition in high vacuum environment, due to relatively costly, is only applied only to microelectronic, and the probability of large-scale application is less.Accumulation type solid lithium battery uses the laminated sheet such as positive pole powder, electrolyte powder, negative pole mostly, and electrolyte is typically chosen sulfide-based solid electrolyte (Thio-LISICON)；Running into air due to sulfide-based solid electrolyte and moisture is unstable, whole process needs to complete in an inert atmosphere, and technology difficulty is bigger.At present, there is no such business-like product and occur, the highest cost is also to hinder all solid-state thin-film lithium battery to maximize further a big barrier of popularization and application；The sulfide-based solid electrolyte that accumulation type (bulk-type) solid lithium battery uses equally exists the problems such as relatively costly, process operability is poor；The more important thing is that Presence of an interface effect between sulfide-based solid electrolyte and positive electrode greatly affects the performance of all-solid-state battery.Positive electrode Surface coating is one of the strategy alleviating this problem, but due to the factor such as change in volume during electrode material removal lithium embedded, often causes clad to rupture, so still cannot solve the problem of performance degradation in solid lithium battery cyclic process.
Summary of the invention
The present invention is directed to above-mentioned technical problem, propose a kind of lithium ion battery, including battery container and the battery core that is positioned at battery container, described battery core includes positive pole, negative pole and the electrolyte between positive pole and negative pole, it is characterized in that, described electrolyte includes being positioned at the first solid-state electrolyte layer of described positive electrode surface and being positioned at the second solid-state electrolyte layer of described negative terminal surface, and described first solid-state electrolyte layer contacts with described second solid-state electrolyte layer；Described first solid-state electrolyte layer includes that the first binding agent and the first inorganic electrolyte granule, described first inorganic electrolyte granule are NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；Described second solid-state electrolyte layer includes the second binding agent and the second inorganic electrolyte granule, and described second inorganic electrolyte granule is sulfide-based solid electrolyte.
The present invention is by arranging the first solid-state electrolyte layer at positive electrode surface and arranging the second solid-state electrolyte layer in negative terminal surface, and described first solid-state electrolyte layer contacts with described second solid-state electrolyte layer；And first solid-state electrolyte layer include the first binding agent and the first inorganic electrolyte granule, described first inorganic electrolyte granule is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte, described second solid-state electrolyte layer includes the second binding agent and the second inorganic electrolyte granule, and described second inorganic electrolyte granule is sulfide-based solid electrolyte；On the one hand NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte layer can maintain the ionic conduction ability of anelectrode and electrolyte, the side reaction between sulfide-based solid electrolyte and high-voltage anode material can be avoided simultaneously, the performance of high pressure lithium battery has been effectively ensured.And, present inventor is found by great many of experiments, if NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte layer directly contact with negative pole, the most easily reduced by the negative material of electronegative potential, cause electrolyte electronic conductance to increase and cause battery short circuit；In the present invention, between NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte layer and negative pole, also there is sulfide-based solid electrolyte layer, NASICON type inorganic electrolyte can be prevented effectively from and/or Ca-Ti ore type inorganic electrolyte layer is reduced under electronegative potential, and the existence of sulfide-based solid electrolyte layer ensure that the normal performance of electronegative potential capacity of negative plates, additionally, the electrolyte of double-layer structure barrier layer each other, can effectively block the side reaction each brought because of potential problem, ensure high voltage and the high-energy-density of battery, it is beneficial to improve battery safety height and cycle performance.
The lithium ion battery prepared by the present invention, not only safety is high, and has higher capacity and good cycle performance.
Present invention further proposes the preparation method of a kind of lithium ion battery, including:
(1) providing positive pole and negative pole, described positive pole includes plus plate current-collecting body and is positioned at the positive electrode of anode collection surface, and described negative pole includes negative current collector and is positioned at the negative material of negative pole currect collecting surface；
(2) preparing electrolyte between described positive pole and negative pole, described electrolyte includes being positioned at first solid-state electrolyte layer on described positive electrode surface and being positioned at second solid-state electrolyte layer on described negative material surface；
(3) the first solid-state electrolyte layer is contacted with the second solid-state electrolyte layer, compressing is placed in battery container encapsulation and obtains lithium ion battery.
Lithium ion battery prepared by the present invention, it is possible to realize higher energy density, high security and preferable cycle performance.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The lithium ion battery that the present invention provides, including battery container and the battery core that is positioned at battery container, described battery core includes positive pole, negative pole and the electrolyte between positive pole and negative pole, described electrolyte includes being positioned at the first solid-state electrolyte layer of described positive electrode surface and being positioned at the second solid-state electrolyte layer of described negative terminal surface, and described first solid-state electrolyte layer contacts with described second solid-state electrolyte layer；Described first solid-state electrolyte layer includes that the first binding agent and the first inorganic electrolyte granule, described first inorganic electrolyte granule are NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；Described second solid-state electrolyte layer includes the second binding agent and the second inorganic electrolyte granule, and described second inorganic electrolyte granule is sulfide-based solid electrolyte.
In the lithium ion battery of the present invention, the positive pole for lithium ion battery is not particularly limited, and can use the positive pole generally used in existing lithium ion battery；Concrete, described positive pole includes plus plate current-collecting body and is positioned at the positive electrode of anode collection surface.
Wherein, the plus plate current-collecting body that plus plate current-collecting body is known to those skilled in the art, such as can be selected from aluminium foil or aluminium foil.
Described positive electrode includes positive active material, positive conductive agent and the 3rd binding agent, and described positive active material is selected from LiNi0.5Mn1.5O4、LiMn2O4、LiCoPO4、LiNiPO4、Li3V3(PO4)3、LiMnPO4、LiNi1/3Co1/3Mn1/3O2In one or more；The conductive agent in lithium ion cell positive that described positive conductive agent is known to the skilled person, the concrete end, described positive conductive agent can be selected from least one in acetylene black, CNT, HV, carbon black；The binding agent in lithium ion cell positive that described 3rd binding agent is known to the skilled person, specifically, described binding agent can be selected from one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).
Between positive electrode and electrolyte that the present invention selects, there is good interface compatibility, be provided simultaneously with higher voltage, it is possible to achieve high-energy-density.Particularly current electrolyte system cannot meet high-voltage anode material demand, causes the lithium ion battery of liquid electrolyte liquid system to be difficult to further and improves its energy density；Solid electrolyte is expected to thoroughly improve this problem.
In above-mentioned positive electrode, the content of positive conductive agent and the 3rd binding agent is known to the skilled person, and specifically, on the basis of the weight of positive active material, the content of conductive agent is 0.1-20wt%, preferably 1-10wt%；The content of the 3rd binding agent is 0.01-10wt%, preferably 0.02-5wt%.
In the lithium ion battery of the present invention, it is preferable that also include additive in described positive electrode, described additive is selected from LiNbO3、LiTaO3、Lix1La1/(3-x1)TaO3、Li3PO4、Lix2Tiy2(PO4)3、Lix3Aly3Tiz3(PO4)3、Li2SiO3、Li2O、Li2S、Li2S-P2S5、Li2S-SiS2-P2S5、Lix4Siy4Sz4、Lix5Py5Sz5、LiBO2、Li3.6Si0.6P0.4O4In one or more, wherein, 0 ＜ x1＜ 3；0 ＜ x2＜ 2,0 ＜ y2＜ 3；0 ＜ x3＜ 2,0 ＜ y3＜ 1,0 ＜ z3＜ 3；0 ＜ x4＜ 3,0 ＜ y4＜ 2,0 ＜ z4＜ 4；0 ＜ x5＜ 3,0 ＜ y5＜ 3,0 ＜ z5＜ 7；Described non-additive content is 0.1-50wt%, preferably 0.5-20wt%.
All-solid-state battery does not exist wettable electrolyte, ionic conduction between electrode particle cannot be carried out by being similar to the bridge joint effect of electrolyte, the addition of additive can alleviate this technical problem, by adding above-mentioned additive in positive electrode, the lithium ion battery prepared also has more preferable charge-discharge performance and cycle performance.
In the lithium ion battery of the present invention, the negative pole of lithium ion battery is not particularly limited, can be the negative pole generally used in existing lithium ion battery；Concrete, described negative pole includes negative current collector and is positioned at the negative material of described negative pole currect collecting surface.
The negative current collector that described negative current collector is known to the skilled person, for example, it is possible to selected from aluminium foil or Copper Foil.
Described negative material includes negative electrode active material and the 4th binding agent；Described negative electrode active material can be the negative electrode active material that this area is conventional；Concrete, one or more in material with carbon element, ashbury metal, silicon alloy, silicon, stannum, germanium of described negative electrode active material；Further, described material with carbon element can be selected from one or more in native graphite, natural modified graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal and silicon alloy, preferably Delanium and natural modified graphite；Meanwhile, negative electrode active material can also be lithium metal, lithium-indium alloy etc.；Generally, according to actually used situation, described negative material can also contain cathode conductive agent, described cathode conductive agent is not particularly limited, can be the cathode conductive agent of this area routine, such as, can be one or more in carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive black and electrically conductive graphite；The binding agent in lithium ion battery negative that the 4th described binding agent is known in the art, specifically, described 4th binding agent can be selected from polythiophene, polypyrrole, politef, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, one or more in styrene-butadiene latex.
In above-mentioned negative material, the content of negative electrode active material and the 4th binding agent is known to the skilled person, and specifically, on the basis of the weight of described negative electrode active material, the content of described cathode conductive agent is 0.5-10wt%；The content of described 4th binding agent is 0.01-10wt%.
The lithium ion battery that the present invention provides, electrolyte is also included between described positive pole and negative pole, it is characterized in that, described electrolyte includes being positioned at the first solid-state electrolyte layer of described positive electrode surface and being positioned at the second solid-state electrolyte layer of described negative terminal surface, and described first solid-state electrolyte layer contacts with described second solid-state electrolyte layer；Described first solid-state electrolyte layer includes that the first binding agent and the first inorganic electrolyte granule, described first inorganic electrolyte granule are NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；Described second solid-state electrolyte layer includes the second binding agent and the second inorganic electrolyte granule, and described second inorganic electrolyte granule is sulfide-based solid electrolyte.
The lithium ion battery that the present invention provides, wherein, described sulfide-based solid electrolyte is the Li of glassy state2S-P2S5, the Li of crystalline statex ＇My ＇PSz ＇Or the Li of glass ceramics state2S-P2S5In one or more, one or more during wherein M is Si, Ge, Sn, x ＇+4y ＇+5=2z ＇, 0≤y ＇≤1；Wherein Li2S-P2S5Refer to the Li prepared according to a certain percentage2S and P2S5Complex；Preferably, at preparation Li2S-P2S5During complex, described Li2S and P2S5Between mol ratio be 60:40～90:10.
The lithium ion battery proposed according to the present invention, the Li of described glassy state2S-P2S5It is preferably the Li of glassy state7P3S11, the 70Li of glassy state2S-30P2S5In one or both.
In the present invention, the Li of glassy state2S-P2S5Refer to Li2S-P2S5In glassy state, the Li of crystalline statex ＇My ＇PSzRefer to Lix ＇My ＇PSzIn crystalline state, the Li of glass ceramics state2S-P2S5Refer to Li2S-P2S5In glass ceramics state, the Li of glass state7P3S11Refer to Li7P3S11In glassy state, the 70Li of glassy state2S-30P2S5Refer to 70Li2S-30P2S5In glassy state.
The lithium ion battery that the present invention provides, wherein said NASICON type inorganic electrolyte is LiM2(PO4)3And one or more in alloy, wherein, M is selected from Ti, Zr, Ge, Sn or Pb, one or more in Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V of the doped chemical in described alloy；
Described Ca-Ti ore type inorganic electrolyte has following composition: AxByTiO3、AxByTa2O6、AxByNb2O6, or AhMkDnTiwO3；Wherein x+3y=2, h+2k+5n+4w=6,0 ＜ x ＜ 2,0 ＜ y ＜ 2/3, h, k, n, w are all higher than 0；One or more in Li, Na element of A, one or more in La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element of B, one or more in Sr, Ca, Ba, Ir, Pt element of M, one or more in Nb, Ta element of D.
The lithium ion battery proposed according to the present invention, it is further preferred that the thickness of above-mentioned first solid-state electrolyte layer is 1-50 μm, the thickness of above-mentioned second solid-state electrolyte layer is 1-50 μm；First solid-state electrolyte layer and the second solid-state electrolyte layer are set to this thickness, on the one hand can stop the electronic conduction between both positive and negative polarity, prevent short circuit；On the other hand the ionic conduction between both positive and negative polarity can be maintained, it is ensured that the energy output of battery.
The lithium ion battery provided according to the present invention, it is further preferred that in the first solid-state electrolyte layer, on the basis of the gross weight of described first solid-state electrolyte layer, the content of described first inorganic electrolyte granule is 80%-99.5%；In the second solid-state electrolyte layer, on the basis of the gross weight of described second solid-state electrolyte layer, the content of described second inorganic electrolyte granule is 80%-99.5%.
The lithium ion battery provided according to the present invention, further, in described first solid-state electrolyte layer, on the basis of the gross weight of described first solid-state electrolyte layer, the content of described first binding agent is 0.5%-20%；In described second solid-state electrolyte layer, on the basis of the gross weight of described second solid-state electrolyte layer, the content of described second binding agent is 0.5%-20%.
Further, described first binding agent, the second binding agent are independently selected from one or more in polythiophene, polypyrrole, politef, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethyl cellulose, styrene-butadiene latex.
Invention further provides the preparation method of a kind of lithium ion battery, including:
(1) providing positive pole and negative pole, described positive pole includes plus plate current-collecting body and is positioned at the positive electrode of anode collection surface, and described negative pole includes negative current collector and is positioned at the negative material of negative pole currect collecting surface；
(2) preparing electrolyte between described positive pole and negative pole, described electrolyte includes being positioned at first solid-state electrolyte layer on described positive electrode surface and being positioned at second solid-state electrolyte layer on described negative material surface；
(3) the first solid-state electrolyte layer is contacted with the second solid-state electrolyte layer, compressing is placed in battery container encapsulation and obtains lithium ion battery.
Preparation method according to the lithium ion battery that the present invention proposes, it is characterised in that the method farther includes: prepare the first solid-state electrolyte layer on the surface of described positive electrode；The second solid-state electrolyte layer is prepared on the surface of described first solid-state electrolyte layer；Described negative pole is placed in the surface of described second solid-state electrolyte layer, compressing.
Preparation method according to the lithium ion battery that the present invention proposes, it is characterized in that, described first solid-state electrolyte layer includes that the first binding agent and the first inorganic electrolyte granule, described first inorganic electrolyte granule are NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；Described second solid-state electrolyte layer includes the second binding agent and the second inorganic electrolyte granule, and described second inorganic electrolyte granule is sulfide-based solid electrolyte.
Preparation method according to the lithium ion battery that the present invention proposes, further preferably, the method preparing the first solid-state electrolyte layer on the surface of described positive electrode includes: at surface-coated the first solid electrolyte slurry of described positive electrode, then dry at 50-200 DEG C, tabletting, form described first solid-state electrolyte layer on described positive electrode surface, obtain positive pole and the complex of the first solid-state electrolyte layer；Wherein, described first solid electrolyte slurry includes being mixed to get the first binding agent, the first inorganic electrolyte granule and the first solvent, and described first inorganic electrolyte granule is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；On the basis of the gross weight of described first solid electrolyte slurry, the content of described first binding agent is 0.5%-20%, and the content of described first solvent is 20%-350%；Wherein, one or more in polythiophene, polypyrrole, politef, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethyl cellulose (CMC), styrene-butadiene latex (SBR) of the first binding agent；One or more in N-Methyl pyrrolidone, water, ethanol, acetone of first solvent；Preparing the first solid-state electrolyte layer on the surface of positive electrode, the thickness of the first solid-state electrolyte layer prepared is 1-50 μm.
The lithium ion battery proposed according to the present invention, further preferably, the method preparing the second solid-state electrolyte layer on the surface of described first solid-state electrolyte layer includes: at surface-coated the second solid electrolyte slurry of the first solid-state electrolyte layer in glove box, then dry at 50-200 DEG C, tabletting, form described second solid-state electrolyte layer on the surface of described first solid-state electrolyte layer, obtain positive pole, the first solid-state electrolyte layer, the complex of the second solid-state electrolyte layer three-decker；Wherein, described second solid electrolyte slurry includes being mixed to get the second binding agent, the second inorganic electrolyte granule and the second solvent；Described second inorganic electrolyte granule is sulfide-based solid electrolyte；On the basis of the gross weight of described second solid electrolyte slurry, the content of described second binding agent is 0.5%-20%, the content of described second solvent is 20%-350%, wherein, second binding agent is selected from polythiophene, polypyrrole, politef, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethyl cellulose (CMC), one or more in styrene-butadiene latex (SBR)；One or more in N-Methyl pyrrolidone, water, ethanol, acetone of second solvent；The thickness of the second solid-state electrolyte layer prepared is 1-50 μm.
Above-mentioned positive pole by buying or can be prepared voluntarily, and the preparation method of positive pole is known to the skilled person, such as, be coated on plus plate current-collecting body by anode sizing agent, and drying, calendering prepare positive pole；Wherein, anode sizing agent includes that positive active material, positive conductive agent, the 3rd binding agent and positive pole solvent are mixed to get, and wherein, positive active material, positive conductive agent, the 3rd binding agent and content thereof are as it was noted above, again repeat no more；Positive active material, positive conductive agent, the 3rd binding agent are mixed to get anode sizing agent with positive pole solvent, then anode sizing agent is coated on plus plate current-collecting body and dries, in drying course, the volatilization of positive pole solvent is removed, material and the amount of interpolation that described positive pole solvent is used are known to those skilled in the art, again repeat no more.
Preferably, in the preparation process of above-mentioned positive pole, also can add inorganic solid electrolyte additive in anode sizing agent, described inorganic solid electrolyte additive is selected from LiNbO3、LiTaO3、Lix1La1/(3-x1)TaO3、Li3PO4、Lix2Tiy2(PO4)3、Lix3Aly3Tiz3(PO4)3、Li2SiO3、Li2O、Li2S、Li2S-P2S5、Li2S-SiS2-P2S5、Lix4Siy4Sz4、Lix5Py5Sz5、LiBO2、Li3.6Si0.6P0.4O4In one or more, wherein, 0 ＜ x1＜ 3；0 ＜ x2＜ 2,0 ＜ y2＜ 3；0 ＜ x3＜ 2,0 ＜ y3＜ 1,0 ＜ z3＜ 3；0 ＜ x4＜ 3,0 ＜ y4＜ 2,0 ＜ z4＜ 4；0 ＜ x5＜ 3,0 ＜ y5＜ 3,0 ＜ z5＜ 7；The content of described inorganic solid electrolyte additive is 0.1-50wt%, preferably 0.5-20wt%.
After preparing positive pole, prepare the first solid-state electrolyte layer on the surface of positive electrode, after the first solid-state electrolyte layer is prepared on the surface of positive pole, prepare the second solid-state electrolyte layer on the surface of described first solid-state electrolyte layer；Negative pole is provided, negative pole is placed in the surface of described second solid-state electrolyte layer, compressing after, be placed in encapsulation in battery container and obtain the lithium ion battery of the present invention.
Described negative pole by buying or can be prepared, the preparation method that the preparation method of negative pole is known to the skilled person voluntarily, such as, be coated on negative current collector by cathode size, and drying, calendering prepare negative pole；Wherein, cathode size includes being mixed to get negative electrode active material, the 4th binding agent with negative pole solvent, and wherein, negative electrode active material and the concrete substance classes of the 4th binding agent and content thereof be not as it was previously stated, repeat them here；Preferably, can also add cathode conductive agent in described cathode size, the content of described cathode conductive agent is 0.5-10wt%；Negative electrode active material, the 4th binding agent are mixed to get cathode size with negative pole solvent, then cathode size is coated on negative current collector and dries, in drying course, the volatilization of negative pole solvent is removed, material and the amount of interpolation that described negative pole solvent is used are known to those skilled in the art, again repeat no more.
Preparation method according to the lithium ion battery that the present invention provides, in the above-mentioned methods, negative pole is placed in the surface of the second solid-state electrolyte layer, compressing it is placed in battery container encapsulation and obtains lithium ion battery, the method for packing of the battery that described method for packing is known to the skilled person, does not repeats them here.
The preparation method of lithium ion battery provided according to invention, in above-mentioned steps (3), described compressing method is: at 50-300 DEG C, hot pressing 0.05-10h under 0.1-50MPa.
In the application, lithium ion battery can also be prepared: provides positive pole, at the above-mentioned first solid electrolyte slurry of positive electrode surface-coated, then dries at 50-200 DEG C, tabletting, forms described first solid-state electrolyte layer on described positive electrode surface；Negative pole is provided, at the above-mentioned second solid electrolyte slurry of negative material surface-coated, then dries at 50-200 DEG C, tabletting, form described second solid-state electrolyte layer on the surface of described negative material；Then the first solid-state electrolyte layer is contacted with the second solid-state electrolyte layer, compressing obtain lithium ion battery.
By the following examples the present invention is described in more detail.
Embodiment 1
The preparation of positive pole:
By 930 grams of positive electrode active materials LiNi0.5Mn1.5O4(93%), 30 grams of bonding agent PVDF(3%), 20 grams of acetylene blacks (2%), 20g conductive agent HV(2%) join 1500 grams of solvent NMP(N-methyl ketopyrrolidines) in, then in de-airing mixer stir, formed stable uniform anode sizing agent.This anode sizing agent interval being equably coated on the two sides of aluminium foil (aluminium foil a size of: width 160 millimeters, thickness 16 microns), then 120 DEG C of drying, obtain positive pole after roll squeezer tabletting；
The preparation of the first solid electrolyte:
By the inorganic solid electrolyte material Li of 950 grams1.3Al0.3Ti1.7(PO4)3(95%), the binding agent SBR(5% of 5 grams) join in 1000 grams of deionized waters, then stir in de-airing mixer, form the first solid electrolyte slurry of stable uniform, on the surface of the positive electrode that this first solid electrolyte slurry is coated on the positive pole that step 1 obtains continuously, then 120 DEG C of drying, through roll squeezer tabletting, positive pole forms the first solid-state electrolyte layer；Wherein, the thickness of the first solid-state electrolyte layer is 40 μm；
The preparation of the second solid-state electrolyte layer:
In glove box, by the 70Li of the glassy state of 600 grams2S-30P2S5Add in the toluene solution of 1200 grams, wherein containing 30g butadiene rubber binding agent in toluene solution, then heated and stirred obtains the second solid electrolyte slurry, this the second solid electrolyte slurry is coated on continuously the surface of above-mentioned first solid electrolyte, then 60 DEG C of drying, cut out as 485(length) × 46(width) size；Wherein, the thickness of the second solid-state electrolyte layer is 20 μm；
The preparation of negative pole:
By 940 grams of negative active core-shell material Delaniums (94%), 30 grams of bonding agent CMC(3%) and 30 grams of bonding agent SBR(3%) join in 1200 grams of deionized waters, then stir in de-airing mixer, form the cathode size of stable uniform, this cathode size interval equably is coated on Copper Foil (aluminium foil a size of: width 160 millimeters, thickness 16 microns) two sides on, then 120 DEG C of drying, after roll squeezer tabletting, cut out as 480(length) × 45(width) negative plate of size；
In glove box, above-mentioned negative plate is placed in the surface of the second solid electrolyte, after cutting out, alignment is placed in hot press, carry out 150 DEG C of hot pressing 1 hour, aluminum plastic film vacuum-pumping density is used to be honored as a queen, take out sample, isostatic pressing machine i.e. obtains after 200MPa, 300S suppress the lithium ion battery S1 of the present embodiment.
Embodiment 2
Using method same as in Example 1 to prepare lithium ion battery, difference is, during preparing the first solid-state electrolyte layer, uses Li0.5La0.5TiO3Replace the Li in embodiment 11.3Al0.3Ti1.7(PO4)3, other are the most same as in Example 1, prepare lithium ion battery S2.
Embodiment 3
Using method same as in Example 1 to prepare lithium ion battery, difference is, during preparing the second solid-state electrolyte layer, uses 80Li2S-20P2S5Glass ceramics replaces the 70Li of the glassy state in embodiment 12S-30P2S5, prepare lithium ion battery S3.
Embodiment 4
Using method same as in Example 1 to prepare lithium ion battery, difference is, during preparing the first solid-state electrolyte layer, uses Li0.35La0.55TiO3Replace the Li in embodiment 11.3Al0.3Ti1.7(PO4)3, prepare lithium ion battery S4.
Embodiment 5
Using method same as in Example 1 to prepare lithium ion battery, difference is, during preparing the second solid-state electrolyte layer, with the Li of crystalline state10SnP2S12The 70Li of the glassy state in replacement embodiment 12S-30P2S5, prepare lithium ion battery S5.
Embodiment 6
Using method same as in Example 1 to prepare lithium ion battery, difference is, during preparing positive pole, and positive active material LiNiPO4Replace LiNi0.5Mn1.5O4, prepare lithium ion battery S6.
Embodiment 7
Using method same as in Example 1 to prepare lithium ion battery, difference is, the thickness of described first dielectric substrate is 15 μm, and the thickness of described second dielectric substrate is 10 μm, prepares lithium ion battery S7.
Embodiment 8
Using method same as in Example 1 to prepare lithium ion battery, difference is, the thickness of described first dielectric substrate is 5 μm, and the thickness of described second dielectric substrate is 35 μm, prepares lithium ion battery S8.
Comparative example 1
The polypropylene diaphragm that positive pole same as in Example 1, negative pole and thickness are 20 μm is wound into the battery core of rectangular lithium ion battery, is then passed through fluid injection, seals, be aged, be melted into, i.e. obtain lithium ion battery DS1 after partial volume.
Comparative example 2
Preparation method is substantially the same manner as Example 1, and difference is, does not prepares the first solid-state electrolyte layer, and directly the second solid-state electrolyte layer is prepared on the surface at negative or positive electrode, obtains lithium ion battery DS2.
Comparative example 3
Preparation method is substantially the same manner as Example 1, and difference is, does not prepares the second solid-state electrolyte layer, and directly the first solid-state electrolyte layer is prepared on the surface at negative or positive electrode, obtains lithium ion battery DS3.
Performance test
The battery each embodiment and comparative example prepared respectively takes 20, on LAND CT 2001C secondary cell device for detecting performance, under the conditions of 25 ± 1 DEG C, with 0.0.1C, battery is carried out charge and discharge cycles test.Step is as follows: shelve 10min；Constant-voltage charge ends to 5V/0.05C；Shelve 10min；Constant-current discharge, to 3.0V, is 1 circulation.Repeating this step, in cyclic process when battery capacity is less than the 80% of discharge capacity first, loop termination, this cycle-index is the cycle life of battery, and often group is averaged.
Test result is as follows:
The circulating battery of embodiment 1 preparation 650 times；
The circulating battery of embodiment 2 preparation 532 times；
The circulating battery of embodiment 3 preparation 634 times；
The circulating battery of embodiment 4 preparation 628 times；
The circulating battery of embodiment 5 preparation 438 times；
The circulating battery of embodiment 6 preparation 395 times；
The circulating battery of embodiment 7 preparation 682 times；
The circulating battery of embodiment 8 preparation 352 times；
The circulating battery of comparative example 1 preparation is less than 5 times, and percentage of batteries continues aerogenesis to battery swell in cyclic process, and then catches fire；
Being short-circuited during the battery initial charge of comparative example 2 preparation, voltage continuous decrease is zero, it is impossible to be circulated；
The circulating battery of comparative example 3 preparation 35 times.
By above-mentioned test: all solid state high voltage lithium battery electric core that the present invention provides has cycle performance and the security performance of excellence, a series of security performances and the problem of one-component inorganic solid electrolyte cycle performance difference that liquid electrolyte causes can be prevented effectively from.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.

Claims (16)

1. a lithium ion battery, including battery container and the battery core that is positioned at battery container, described battery core includes positive pole, negative pole and the electrolyte between positive pole and negative pole, it is characterized in that, described electrolyte includes being positioned at the first solid-state electrolyte layer of described positive electrode surface and being positioned at the second solid-state electrolyte layer of described negative terminal surface, and described first solid-state electrolyte layer contacts with described second solid-state electrolyte layer；Described first solid-state electrolyte layer includes that the first binding agent and the first inorganic electrolyte granule, described first inorganic electrolyte granule are NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；Described second solid-state electrolyte layer includes the second binding agent and the second inorganic electrolyte granule, and described second inorganic electrolyte granule is sulfide-based solid electrolyte.
Lithium ion battery the most according to claim 1, it is characterised in that described sulfide-based solid electrolyte is the Li of glassy state2S-P2S5, the Li of crystalline statex ＇My ＇PSz ＇Or the Li of glass ceramics state2S-P2S5In one or more, one or more during wherein M is Si, Ge, Sn, x ＇+4y ＇+5=2z ＇, 0≤y ＇≤1.
Lithium ion battery the most according to claim 2, it is characterised in that the Li of described glassy state2S-P2S5Li including glassy state7P3S11, the 70Li of glassy state2S-30P2S5In one or both.
Lithium ion battery the most according to claim 1, it is characterised in that described NASICON type inorganic electrolyte is LiM2(PO4)3And one or more in alloy, wherein, M is selected from Ti, Zr, Ge, Sn or Pb, one or more in Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V of the doped chemical in described alloy；
Described Ca-Ti ore type inorganic electrolyte has following composition: AxByTiO3、AxByTa2O6、AxByNb2O6, or AhMkDnTiwO3；Wherein x+3y=2, h+2k+5n+4w=6,0 ＜ x ＜ 2,0 ＜ y ＜ 2/3, h, k, n, w are all higher than 0；One or more in Li, Na element of A, one or more in La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element of B, one or more in Sr, Ca, Ba, Ir, Pt element of M, one or more in Nb, Ta element of D.
Lithium ion battery the most according to claim 1, it is characterised in that the thickness of described first solid-state electrolyte layer is 1-50 μm, the thickness of described second solid-state electrolyte layer is 1-50 μm.
Lithium ion battery the most according to claim 1, it is characterised in that in the first solid-state electrolyte layer, on the basis of the gross weight of described first solid-state electrolyte layer, the content of described first inorganic electrolyte granule is 80%-99.5%；In the second solid-state electrolyte layer, on the basis of the gross weight of described second solid-state electrolyte layer, the content of described second inorganic electrolyte granule is 80%-99.5%.
Lithium ion battery the most according to claim 1, it is characterised in that in the first solid-state electrolyte layer, on the basis of the gross weight of described first solid-state electrolyte layer, the content of described first binding agent is 0.5%-20%；In the second solid-state electrolyte layer, on the basis of the gross weight of described second solid-state electrolyte layer, the content of described second binding agent is 0.5%-20%.
Lithium ion battery the most according to claim 1, it is characterized in that, described first binding agent, second binding agent is independently selected from polythiophene, polypyrrole, politef, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethyl cellulose, one or more in styrene-butadiene latex.
9., according to the lithium ion battery described in claim 1-8 any one, it is characterised in that described positive pole includes plus plate current-collecting body and the positive electrode being positioned on plus plate current-collecting body, and described positive electrode includes positive active material, described positive active material is selected from LiNi0.5Mn1.5O4、LiMn2O4、LiCoPO4、LiNiPO4、Li3V3(PO4)3 、LiMnPO4、LiNi1/3Co1/3Mn1/3O2In one or more.
Lithium ion battery the most according to claim 9, it is characterised in that also include additive in described positive electrode, described additive is selected from LiNbO3、LiTaO3、Lix1La1/(3-x1)TaO3、Li3PO4、Lix2Tiy2(PO4)3、Lix3Aly3Tiz3(PO4)3、Li2SiO3、Li2O、Li2S、Li2S-P2S5、Li2S-SiS2-P2S5、Lix4Siy4Sz4、Lix5Py5Sz5、LiBO2、Li3.6Si0.6P0.4O4In one or more, wherein, 0 ＜ x1＜ 3；0 ＜ x2＜ 2,0 ＜ y2＜ 3；0 ＜ x3＜ 2,0 ＜ y3＜ 1,0 ＜ z3＜ 3；0 ＜ x4＜ 3,0 ＜ y4＜ 2,0 ＜ z4＜ 4；0 ＜ x5＜ 3,0 ＜ y5＜ 3,0 ＜ z5＜ 7.
The preparation method of 11. 1 kinds of lithium ion batteries, including:
(1) providing positive pole and negative pole, described positive pole includes plus plate current-collecting body and is positioned at the positive electrode of anode collection surface, and described negative pole includes negative current collector and is positioned at the negative material of negative pole currect collecting surface；
(2) preparing electrolyte between described positive pole and negative pole, described electrolyte includes being positioned at first solid-state electrolyte layer on described positive electrode surface and being positioned at second solid-state electrolyte layer on described negative material surface；
(3) the first solid-state electrolyte layer is contacted with the second solid-state electrolyte layer, compressing is placed in battery container encapsulation and obtains lithium ion battery.
The preparation method of 12. lithium ion batteries according to claim 11, it is characterised in that including: prepare the first solid-state electrolyte layer on the surface of described positive electrode；The second solid-state electrolyte layer is prepared on the surface of described first solid-state electrolyte layer；Described negative pole is placed in the surface of described second solid-state electrolyte layer, compressing.
13. according to the preparation method of the lithium ion battery described in claim 11-12 any one, it is characterized in that, described first solid-state electrolyte layer includes that the first binding agent and the first inorganic electrolyte granule, described first inorganic electrolyte granule are NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；Described second solid-state electrolyte layer includes the second binding agent and the second inorganic electrolyte granule, and described second inorganic electrolyte granule is sulfide-based solid electrolyte.
The preparation method of 14. lithium ion batteries according to claim 12, it is characterized in that, the method preparing the first solid-state electrolyte layer on the surface of described positive electrode includes: at surface-coated the first solid electrolyte slurry of described positive electrode, then dry at 50-200 DEG C, tabletting, forms described first solid-state electrolyte layer on described positive electrode surface；Described first solid electrolyte slurry includes the first binding agent, the first inorganic electrolyte granule and the first solvent.
15. according to the preparation method of the lithium ion battery described in claim 12 or 14 any one, it is characterized in that, the method preparing the second solid-state electrolyte layer on the surface of described first solid-state electrolyte layer includes: at surface-coated the second solid electrolyte slurry of the first solid-state electrolyte layer in glove box, then dry at 50-200 DEG C, tabletting, forms described second solid-state electrolyte layer on the surface of described first solid-state electrolyte layer；Described second solid electrolyte slurry includes the second binding agent, the second inorganic electrolyte granule and the second solvent.
16. according to the preparation method of the lithium ion battery described in claim 14-15 any one, it is characterized in that, described first solvent, the second solvent are independently selected from one or more in N-Methyl pyrrolidone, water, ethanol, acetone, toluene, dimethylbenzene, heptane.
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