CN103746089B - A kind of solid lithium battery with gradient-structure and preparation method thereof - Google Patents

A kind of solid lithium battery with gradient-structure and preparation method thereof Download PDF

Info

Publication number
CN103746089B
CN103746089B CN201310674203.4A CN201310674203A CN103746089B CN 103746089 B CN103746089 B CN 103746089B CN 201310674203 A CN201310674203 A CN 201310674203A CN 103746089 B CN103746089 B CN 103746089B
Authority
CN
China
Prior art keywords
gradient
electrode
layer
lithium battery
molecular weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310674203.4A
Other languages
Chinese (zh)
Other versions
CN103746089A (en
Inventor
刘晋
贾明
李劼
林月
程昀
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201310674203.4A priority Critical patent/CN103746089B/en
Publication of CN103746089A publication Critical patent/CN103746089A/en
Application granted granted Critical
Publication of CN103746089B publication Critical patent/CN103746089B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of 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

Abstract

The invention discloses a kind of solid lithium battery with gradient-structure and preparation method thereof, this solid lithium battery is made up of the negative pole that has positive pole, solid electrolyte layer and the metal negative pole of gradient-structure layer or have a gradient-structure layer, preparation method is the anode sizing agent that first configures different component concentration or granularity or molecular weight, by the concentration gradient of component or granular gradient or molecular weight gradient, anode sizing agent is coated in and on colelctor electrode, prepares electrode layer, coating solid dielectric substrate on electrode layer again, last adhesion metal negative pole, or the cathode size of configuration different component concentration or granularity or molecular weight, by preparing concentration gradient contrary in the method for anode electrode layer or granular gradient or molecular weight gradient, cathode size is coated in and on dielectric substrate, prepares negative electrode layer, last adhesion colelctor electrode, must there is the solid lithium battery of gradient-structure, this preparation method is simple, and the solid lithium battery high rate charge-discharge making is stable, under large electric current, can normally work.

Description

A kind of solid lithium battery with gradient-structure and preparation method thereof
Technical field
The present invention relates to a kind of solid lithium battery with gradient-structure and preparation method thereof, belong to solid state batteryField.
Background technology
Under the background of the dual trend of energy crisis and environmental protection, development new-energy automobile, as electric vehicle(EV), motor vehicle driven by mixed power (HEV) and plug-in hybrid electric vehicle (PHEV), become active demand. And it is electricPond, as the energy storage device of new-energy automobile, has become one of core key technology of new-energy automobile.
Than liquid state electrolyte battery, all-solid-state battery is improving energy content of battery density, is widening operating temperature districtBetween, also there is larger development space the aspect that increases the service life. Since entering 21 century, diversification becomesThe important development direction in secondary cell field, in widening battery applications field, people also more and more pay attention toBattery is carried out to personalized designs, to improve performance and the thermal adaptability of battery.
Be different from liquid battery, the electrolyte of all-solid-state battery and electrode compatibility are poor, the large multiplying power discharging of batteryPoor performance. Electrolyte is electrochemical reaction avtive spot place to the wellability of electrode, is that electronics and ion " are met "The important leverage that passage is unimpeded, and the Low ESR at electrode interface place is the key that determines battery performance. For solid/, there is not much problems in liquid electrode interface, but for solid/liquid/solid interface, because solid electrolyte does not have liquidThe wellability of body electrolyte, the solid state battery made from solid electrolyte, its interface impedance generally also hinders than bodyOne, Chinese People's Anti-Japanese Military and Political College is more than the order of magnitude. Therefore, take into full account that from the structural design of battery electrode contacts with electrolyticalBecome very important.
On the other hand, if cell electrode layer is made up of uniform electrolyte and electrode material in three-dimensional, exist soIn battery discharge procedure, the lithium ion in the electrolyte in active positive electrode material layer is inhaled into electrode activity fastIn material granule, in electrode active material layers the reduction of electrolytical lithium concentration by lithium ion from electrolyteIn layer, spread and supplement. Meanwhile, the electronics of colelctor electrode conducts by conductive material, thereby promotes electrode reaction.Slowly and lithium ion is diffused into the speed of electrode material layer from dielectric substrate with respect to the conduction of electronics. At heightSpeed discharges and recharges down, and the lithium ion of positive electrode material layer is tending towards exhausting, along with the direction to colelctor electrode, and this trendIncrease. The speed of electrode reaction is unable to catch up with in the diffusion of lithium ion, causes occurring larger overvoltage, and battery cannotTheoretical charge/discharge capacity is provided, and the fast charging and discharging performance of battery declines.
Summary of the invention
Be mainly that electrolyte and electrode material concentration are uniformly distributed for cell electrode layer in prior art, existUnder large current rate, in charge or discharge process, Li ion easily exhausts, and causes the battery of charge or discharge capacityThe defect that can reduce, and there is the solid lithium battery of kind electrode layer, electrode becomes with electrolytical contact easilyPoor, interface impedance is very large, and battery cannot high rate charge-discharge, the object of the invention is to be to provide a kind of greatlyRate charge-discharge is stable, the solid lithium battery with gradient-structure that can normally work under large current rate.
Another object of the present invention is to be to provide a kind of process simple, has gradient knot described in low cost preparationThe method of the solid lithium battery of structure.
The invention provides a kind of solid lithium battery with gradient-structure, this solid lithium battery, by havingPositive pole, solid electrolyte layer and the metal negative pole of gradient-structure layer or there is the negative pole composition of gradient-structure layer;Described gradient-structure layer is that component concentration in gradient continually varying electrode layer, component granularity become in gradient continuouslyElectrode layer or the component molecular weight continually varying electrode layer in gradient changed.
Described gradient is that the size of exponential quantity is continuous variation, can be that numerical value is ascending or descendingContinuous variation.
Described component concentration in gradient continually varying electrode layer is preferably the matter of electrode material in electrode layerAmount percent concentration forms the electrode layer progressively reducing to dielectric substrate direction from colelctor electrode.
The described component granularity granularity that continually varying electrode layer is preferably electrode active material is in gradient at electricityIn utmost point layer, form the electrode layer progressively increasing to dielectric substrate direction from colelctor electrode.
Described component molecular weight in gradient continually varying electrode layer is preferably the molecular weight of polyelectrolyteIn electrode layer, form the electrode layer progressively increasing to dielectric substrate direction from colelctor electrode.
Described component concentration in gradient continually varying electrode layer at least comprises the film of two variable concentrations componentsLayer; Be preferably the rete that at least comprises three variable concentrations components; Most preferably be and at least comprise five variable concentrationsThe rete of component.
Described component granularity in gradient continually varying electrode layer at least comprises the film of two different grain size componentsLayer; Be preferably the rete that at least comprises three different grain size components; Most preferably be and at least comprise five different grain sizesThe rete of component.
Described component molecular weight in gradient continually varying electrode layer at least comprises two different molecular weight componentsRete; Be preferably the rete that at least comprises three different molecular weight components; Most preferably be and at least comprise five notWith the rete of molecular weight component.
The thickness of described rete is 1～100 μ m.
Described dielectric substrate thickness is 1～30 μ m.
Positive electrode active materials in described electrode active material comprises LiCoO2Li-Co composite oxides family,LiNiO2Li-Ni composite oxides family, LiMn2O4Li-Mn composite oxides family, and LiFePO4Li-Fe composite oxides family, or as Li (NiCoMn) O2Li-Ni-Mn-Co-O composite oxides,LiMn0.7Fe0.3PO4Iron manganese phosphate for lithium compound etc.; Negative active core-shell material comprises Li4Ti5O12, graphite orLithium metal etc.
Described solid electrolyte layer comprises inorganic electrolyte material layer or polymer electrolyte, inorganic electrolyteMaterial comprises Ca-Ti ore type, LISICON type, NASICON type, stratiform Li3N class, LiPON class,Oxide glass state and chalcogenide glass state electrolyte, polymer electrolyte comprises polyoxyethylene groups electrolysisMatter, polyoxyethylene deriv base electrolyte and polysiloxanes base electrolyte etc.
Solid lithium battery of the present invention can be assembled into the battery of internal series-connection, internal parallel or both mixing,Prepare difform solid lithium battery unit by the mode such as lamination, volume to volume.
The present invention also provides a kind of method of preparing the described solid lithium battery with gradient-structure, comprisesFollowing steps:
A) electrode material of different quality ratio and electrolyte are mixed with to electrode material mass percentage content differentMany groups anode sizing agent; Or varigrained electrode active material is made into electrode material with auxiliary material respectively, thenBe mixed with electrolyte many groups anode sizing agent that electrode active material granularity is different; Or by the height of different molecular weightMolecule electrolyte is mixed with the different many groups positive electrode of polyelectrolyte molecular weight with electrode material; To prepareThe gradient that good many groups anode sizing agent is pressed electrode material mass percent concentration, or electrode active material granularityGradient, or the gradient of polyelectrolyte molecular weight is coated in colelctor electrode surface successively, obtains having gradient knotThe anodal layer of structure;
B) configuration electrolyte slurry, is coated in described electrolyte slurry the gradient-structure that has of a) gainedAnodal layer surface, obtains dielectric substrate;
C) directly at described dielectric substrate surface adhesion metal electrode b); Or starch according to a) preparation is anodalThe many groups of the method preparation cathode sizes of material, will described many group cathode sizes press electrode material mass percent concentration andA) contrary concentration gradient or press electrode active material granularity with a) contrary granular gradient or by high scoreSub-electrolyte molecule amount is coated on dielectric substrate b) successively with a) contrary molecular weight gradient, then adhesionColelctor electrode, must have the solid lithium battery of gradient-structure.
Described auxiliary material comprises conductive material and bonding agent.
Described coating can be the methods such as ink-jet, blade coating or serigraphy.
The anodal layer of the inventive method and the preparation of dielectric substrate, can also use the sides such as magnetron sputtering, vapour depositionLegal system is standby.
Beneficial effect of the present invention: the electrode layer of electrode in solid lithium battery is designed to tool by first passage of the present inventionThere is the component concentration in gradient to change continuously or component granularity changes in gradient or component molecular weight changes in gradientGradient-structure layer, improves the diffusion rate of lithium ion in electrode layer effectively, and the battery of assembling does not have bright simultaneouslyAobvious solid electrolyte and electrode interface, can realize the Maximum Contact of electrode material and solid electrolyte; HaveThe solid lithium battery of this gradient-structure layer can be realized and discharging and recharging under large multiplying power, also can be normal under large current rateWork; In addition the individual layer battery that, has this gradient-structure layer can be prepared lamination or convoluted various shapeBattery.
Brief description of the drawings
The solid lithium battery schematic diagram that [Fig. 1] prepared for the embodiment of the present invention 1.
The solid lithium battery that [Fig. 2] prepared for the embodiment of the present invention 1 with and comparative example prepare all solid stateLithium battery is at the charging and discharging curve of room temperature 1C multiplying power.
The solid lithium battery schematic diagram that [Fig. 3] prepared for the embodiment of the present invention 2.
The solid lithium battery schematic diagram that [Fig. 4] prepared for the embodiment of the present invention 3.
The solid lithium battery schematic diagram that [Fig. 5] prepared for the embodiment of the present invention 4.
[Fig. 6] is the stacked solid lithium battery schematic diagram of cylindrical interior string: 61 for cell integrated; 62 is negative poleExit; 63 is negative pole coating; 64 is anodal coating; 65 is solid electrolyte; 66 is colelctor electrode; 67For insulating barrier; 68 is anodal exit; 69 is battery case.
[Fig. 7] is the stacked solid lithium battery schematic diagram of square interior string: 71 is anodal exit; 72 is shell;73 is solid electrolyte; 74 is colelctor electrode interlayer dielectic; 75 is colelctor electrode and exit insulating materials;76 is negative pole coating; 77 is anodal coating; 78 is negative pole exit.
Detailed description of the invention
The invention is further illustrated by the following examples, and the present invention is not limited only to described embodiment.
Embodiment 1
(a) change the amount that will be added the electrode material and the solid electrolyte that form electrode layer, make electricityThe mass fraction of utmost point material is 10%, 50%, 100%, prepares anode sizing agent. Wherein electrode material is LiFePO4、The mixture of polyvinylidene fluoride and conduction charcoal (mass ratio 8:1:1), electrolyte is polysiloxanes and lithium saltsThe mixture of (mass ratio 8:2), slurry at room temperature has the viscosity of 3cP;
(b) apply colelctor electrode with described multiple anode sizing agent, make positive electrode concentration gradient along with from electrode activeProperty material layer colelctor electrode reduce to anodal layer surface order, thereby the different anode thin film of stacked multiple solid concentrationLayer; Each anode thin film layer thickness is about 50 μ m left and right;
(c) configuration electrolyte slurry, is coated on anodal established thin layer, and thickness is about 15 μ m left sidesRight;
(d) colelctor electrode of containing metal lithium is pressed on the electrolytic thin-membrane of formation, finally encapsulates with battery case.
Fig. 1 has represented to have the solid lithium battery of concentration of component gradient.
Comparative example 1
Identical in experiment condition and embodiment 1, just electrode material and solid electrolyte are mixed and be coated inOn colelctor electrode, make electrode layer, do not form the concentration gradient of electrode material.
The solid lithium battery that embodiment 1 and comparative example 1 make is put into insulating box, and temperature remains on 25DEG C, use charge and discharge device to carry out the test of 1C multiplying power discharging property.
The solid lithium battery discharge rate of embodiment 1 is 73%, and comparative example 1 solid lithium battery is putElectricity rate is 66%, and the former has higher discharge platform, thereby the former battery is more superior. Voltage and capacity closeSystem as shown in Figure 2.
Embodiment 2
(a) mix a certain amount of spinel structure LiMn2O4For positive electrode active materials, a certain amount of acetylene blackAs conductive material, a certain amount of polyvinylidene fluoride is bonding agent, and three's mass ratio is 9:5:5, certainPolysiloxanes and the lithium salts of amount, both ratios are 8:2, make the constituent mass of electrolyte components and electrode materialThan maintaining 7:3, change LiMn2O4Granularity (0.6 μ m), lives thereby preparation is different for 0.1 μ m, 0.3 μ mThe multiple anode sizing agent of property material particle size;
(b) apply colelctor electrode with described multiple anode sizing agent, make positive electrode active materials granularity along with from electrode activeProperty material layer colelctor electrode increase to anodal layer surface order, each anode thin film layer thickness is about 50 μ m left and right;
(c) configuration electrolyte slurry, siloxanes and lithium salts, both ratios are 8:2, are coated in positive pole and formThin layer on, thickness is about 15 about μ m;
(d) mixing a certain amount of graphite is negative active core-shell material, and a certain amount of acetylene black is as conductive material,A certain amount of polyvinylidene fluoride is bonding agent, and three's mass ratio is 9:5:5, a certain amount of polysiloxanes withLithium salts, both ratios are 8:2, make electrolyte components and the constituent mass ratio of electrode material maintain 7:3, change(0.6 μ m), bears thereby prepare the multiple of different activities material particle size the granularity of alexandrite China ink for 0.1 μ m, 0.3 μ mUtmost point slurry;
(e) apply colelctor electrode with described multiple cathode size, make negative electrode active material material granularity along with dielectric substrateSurface reduce to colelctor electrode, thereby the negative film layer of stacked multiple different activities material granularities.
Fig. 3 has represented to have the solid lithium battery of electrode active material granularity.
Embodiment 3
(a) mix a certain amount of LiCoO2For positive electrode active materials, a certain amount of acetylene black is as conductive material,A certain amount of polyvinylidene fluoride is bonding agent, and three's mass ratio is 9:5:5, a certain amount of polyoxyethylene withLithium salts, both ratios are 8:2, make electrolyte components and the constituent mass ratio of electrode material maintain 7:3, changeThe polyoxyethylated molecular weight (8000,400000,4000000) becoming, thus prepare dividing of electrolytic polymerThe multiple anode sizing agent that son amount is different;
(b) apply colelctor electrode with described multiple anode sizing agent, make polyoxyethylene molecular weight along with from colelctor electrode toAnodal layer surface order increases, and each anode thin film layer thickness is about 50 μ m left and right;
(c) configuration electrolyte slurry, polyoxyethylene (molecular weight 4000000) and lithium salts, both ratios are8:2, is coated on anodal established thin layer, and thickness is about 15 μ m left and right.
(d) mixing a certain amount of graphite is negative active core-shell material, and a certain amount of acetylene black is as conductive material,A certain amount of polyvinylidene fluoride is bonding agent, and three's mass ratio is 9:5:5, a certain amount of polyoxyethylene withLithium salts, both ratios are 8:2, make electrolyte components and the constituent mass ratio of electrode material maintain 7:3, changeBecome polyoxyethylated molecular weight (8000,400000,4000000), thereby prepare the molecule of electrolytic polymerMeasure different multiple cathode sizes;
(e) apply colelctor electrode with described multiple cathode size, make polyoxyethylated molecular weight along with dielectric substrateSurface reduce to colelctor electrode, thereby the negative film layer of stacked multiple different activities material granularities.
Fig. 4 has represented to have the solid lithium battery that electrolytic polymer molecular weight gradient changes.
Embodiment 4
(a) mix a certain amount of LiCoO2For positive electrode active materials, a certain amount of acetylene black is as conductive material,A certain amount of polyvinylidene fluoride is bonding agent, and three's mass ratio is 9:5:5, a certain amount of polysiloxanes withLithium salts, makes electrolyte components and the constituent mass ratio of electrode material maintain 7:3, changes polysiloxanes and lithiumThe ratio (8:2,7:3,6:4) of salt, thus prepare the multiple anode sizing agent that electrolyte lithium salinity is different;
(b) apply colelctor electrode with described multiple anode sizing agent, the content of lithium salts is from colelctor electrode to anodal layer surfaceOrder reduces, and each anode thin film layer thickness is about 50 μ m left and right;
(c) configuration electrolyte slurry, polysiloxanes and lithium salts, both ratios are 8:2, are coated in positive pole shapeOn the thin layer becoming, thickness is about 15 μ m left and right;
(d) mixing a certain amount of graphite is negative active core-shell material, and a certain amount of acetylene black is as conductive material,A certain amount of polyvinylidene fluoride is bonding agent, and three's mass ratio is 9:5:5, a certain amount of polysiloxanes withLithium salts, makes electrolyte components and the constituent mass ratio of electrode material maintain 7:3, changes polysiloxanes and lithiumThe ratio (8:2,7:3,6:4) of salt, thus prepare the multiple cathode size that electrolyte lithium salinity is different;
(e) apply colelctor electrode with described multiple cathode size, make lithium salt along with the surface of dielectric substrate is arrivedColelctor electrode increases, thus the negative film layer of stacked multiple different lithium salinity.
Fig. 5 has represented to have the solid lithium battery of electrolyte concentration graded.
Embodiment 5
From inner electrical connection angle, the solid lithium battery forming according to embodiment 1～4 can designBecome internal series-connection battery unit or internal parallel battery unit. Internal series-connection battery has as simple batteryHigh voltage, and have excellent capacity and output characteristics. Preferred according to the solid lithium battery of embodimentManufacture internal series-connection battery. Sheet cell in stacked embodiment 1～4 has electricity in both positive and negative polarity thin layerSeparate matter layer and separate, then encapsulate whole lamination and with the stacking material sealing that forms battery case, only make positive poleBe exposed to outside with negative wire, thereby solid lithium battery unit is provided.

Claims (6)

1. a solid lithium battery with gradient-structure, is characterized in that, by have gradient-structure layer positive pole,Solid electrolyte layer and metal negative pole or there is the negative pole composition of gradient-structure layer; Described gradient-structure layerFor the granularity of electrode active material forms the electricity progressively increasing to dielectric substrate direction from colelctor electrode in electrode layerThe molecular weight of utmost point layer or polyelectrolyte forms from colelctor electrode and progressively increases to dielectric substrate direction in electrode layerLarge electrode layer; The thickness of described solid electrolyte layer is 1～30 μ m.
2. the solid lithium battery with gradient-structure as claimed in claim 1, is characterized in that, described groupPoint granularity in gradient continually varying electrode layer at least comprises the rete of two different grain size components; Described componentMolecular weight in gradient continually varying electrode layer at least comprises the rete of two different molecular weight components.
3. the solid lithium battery with gradient-structure as claimed in claim 2, is characterized in that, described groupPoint granularity in gradient continually varying electrode layer at least comprises the rete of three different grain size components; Described componentMolecular weight in gradient continually varying electrode layer at least comprises the rete of three different molecular weight components.
4. the solid lithium battery with gradient-structure as claimed in claim 3, is characterized in that, described groupPoint granularity in gradient continually varying electrode layer at least comprises the rete of five different grain size components; Described componentMolecular weight in gradient continually varying electrode layer at least comprises the rete of five different molecular weight components.
5. the solid lithium battery with gradient-structure as claimed in claim 4, is characterized in that, described filmThe thickness of layer is 1～100 μ m.
6. prepare a method for the solid lithium battery with gradient-structure as described in claim 1～5 any one,It is characterized in that, comprise the following steps:
A) varigrained electrode active material is made into electrode material with auxiliary material respectively, then is mixed with electricity with electrolyteMany groups anode sizing agent that utmost point active material granularity is different; Or by the polyelectrolyte of different molecular weight and electrodeMaterial formulation becomes the different many groups positive electrode of polyelectrolyte molecular weight; By the many groups anode sizing agent preparingPress the gradient of electrode active material granularity, or the gradient of polyelectrolyte molecular weight is coated in colelctor electrode successivelySurface, obtains having the anodal layer of gradient-structure;
B) configuration electrolyte slurry, is coated in a) positive pole with gradient-structure of gained by described electrolyte slurryLayer surface, obtains dielectric substrate;
C) directly at described dielectric substrate surface adhesion metal electrode b); Must there is all solid state of gradient-structureLithium battery.
CN201310674203.4A 2013-12-11 2013-12-11 A kind of solid lithium battery with gradient-structure and preparation method thereof Active CN103746089B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310674203.4A CN103746089B (en) 2013-12-11 2013-12-11 A kind of solid lithium battery with gradient-structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310674203.4A CN103746089B (en) 2013-12-11 2013-12-11 A kind of solid lithium battery with gradient-structure and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103746089A CN103746089A (en) 2014-04-23
CN103746089B true CN103746089B (en) 2016-05-11

Family

ID=50503094

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310674203.4A Active CN103746089B (en) 2013-12-11 2013-12-11 A kind of solid lithium battery with gradient-structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103746089B (en)

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101558775B1 (en) * 2014-05-26 2015-10-07 현대자동차주식회사 A method for manufacturing all solid electrode comprising solid electrolyte with concentration gradient
CN105374980B (en) * 2014-08-15 2021-07-13 北京卫蓝新能源科技有限公司 Interface-infiltrated quasi-solid alkali metal battery, battery electrode and battery preparation method
DE102014216423A1 (en) * 2014-08-19 2016-02-25 Robert Bosch Gmbh Electrode for an energy storage and method of manufacture
CN105932335B (en) * 2016-05-04 2019-02-01 上海大学 The preparation method of the conduction energy storage material chip of Organic-inorganic composite containing lithium
KR102202013B1 (en) * 2016-11-21 2021-01-12 주식회사 엘지화학 An electrode for an electrochemical device and a method for manufacturing the same
CN106654367B (en) * 2016-12-19 2020-11-24 天津力神电池股份有限公司 Method for preparing electrolyte membrane and solid lithium battery
CN106785028A (en) * 2016-12-19 2017-05-31 天津力神电池股份有限公司 Application of the chitosan polymer in terms of solid electrolyte membrane
CN106684444A (en) * 2016-12-19 2017-05-17 天津力神电池股份有限公司 Solid state polymer electrolyte membrane
KR101796259B1 (en) * 2017-03-28 2017-11-10 주식회사 세븐킹에너지 Hybrid Solid Electrolyte of Multi Layer and Battery Using the Same
CN109509872B (en) * 2017-09-14 2021-01-01 中南大学 All-solid-state lithium sulfur/sodium sulfur battery with halide serving as electrode active substance and catalyst
CN111712942A (en) * 2018-01-08 2020-09-25 24M技术公司 Electrochemical cell including a permselective membrane, system, and method of making same
CN108258323B (en) * 2018-01-30 2019-09-10 陕西煤业化工技术研究院有限责任公司 A kind of production method of high specific energy solid lithium battery
CN111293287B (en) * 2018-12-09 2021-10-08 中国科学院大连化学物理研究所 Lithium metal negative electrode and preparation and application thereof
CN111864258A (en) * 2019-04-26 2020-10-30 日立化成株式会社 Solid composite electrolyte membrane, method for producing same, and polymer secondary battery
US11631920B2 (en) 2019-06-27 2023-04-18 24M Technologies, Inc. Dual electrolyte electrochemical cells, systems, and methods of manufacturing the same
CN110350238A (en) * 2019-07-03 2019-10-18 中兴高能技术有限责任公司 A kind of all-solid lithium-ion battery and preparation method thereof with porous gradient-structure
CN110380133A (en) * 2019-08-02 2019-10-25 中南大学 A kind of transition zone design method of inorganic solid electrolyte and positive interpolar
CN110660965B (en) * 2019-08-29 2021-12-17 孚能科技(赣州)股份有限公司 Negative plate and preparation method thereof, lithium ion battery and preparation method and application thereof
CN110571406B (en) * 2019-09-12 2020-12-15 泰州纳新新能源科技有限公司 Preparation method of carbon material cathode for lithium ion battery
JP7238734B2 (en) * 2019-11-13 2023-03-14 トヨタ自動車株式会社 Method for manufacturing all-solid-state battery and all-solid-state battery
CN112864374B (en) * 2019-11-27 2022-06-03 郑州宇通集团有限公司 Lithium cathode with gradient distribution of lithium content, preparation method thereof and lithium secondary battery
CN110931743B (en) * 2019-11-29 2022-03-08 桂林电子科技大学 Composite electrode material and preparation method and application thereof
CN111092261B (en) * 2019-12-12 2021-04-02 中国第一汽车股份有限公司 Solid-state battery electrode unit
CN111081975B (en) * 2019-12-30 2021-11-05 国联汽车动力电池研究院有限责任公司 Battery pole piece, preparation method thereof and battery containing pole piece
CN111312992A (en) * 2020-02-26 2020-06-19 天津国安盟固利新材料科技股份有限公司 Multifunctional composite positive plate for secondary battery, preparation method and secondary battery
CN111312991A (en) * 2020-02-29 2020-06-19 天津国安盟固利新材料科技股份有限公司 Chargeable and dischargeable solid battery and preparation method and application thereof
CN111477841A (en) * 2020-05-26 2020-07-31 苏州凌威新能源科技有限公司 Lithium battery pole piece and preparation method thereof
CN113839028B (en) * 2020-06-24 2023-02-10 比亚迪股份有限公司 Positive plate and battery
CN111755664B (en) * 2020-06-30 2022-09-06 蜂巢能源科技股份有限公司 Electrode of lithium ion battery and lithium ion battery
CN112151856A (en) * 2020-11-02 2020-12-29 武汉理工大学 Organic/inorganic composite solid electrolyte with gradient interface structure and all-solid-state lithium battery
CN114597348A (en) 2020-12-02 2022-06-07 通用汽车环球科技运作有限责任公司 Method for producing electrode by rolling
CN114597346A (en) * 2020-12-02 2022-06-07 通用汽车环球科技运作有限责任公司 Thick electrodes for electrochemical cells
CN113690498A (en) * 2021-07-30 2021-11-23 东莞凯德新能源有限公司 Composite negative plate and lithium ion battery comprising same
CN113725399A (en) * 2021-08-26 2021-11-30 湖北亿纬动力有限公司 Battery pole piece with multilayer structure and preparation method thereof
CN115064655B (en) * 2022-06-29 2024-02-09 中汽创智科技有限公司 All-solid-state battery pole piece and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1415121A (en) * 1999-10-22 2003-04-30 三洋电机株式会社 Electrode for lithium cell and rechargeable lithium cell

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060251965A1 (en) * 2003-07-31 2006-11-09 Mori Nagayama Secondary cell electrode and fabrication method, and secondary cell, complex cell, and vehicle
JP5333184B2 (en) * 2009-03-16 2013-11-06 トヨタ自動車株式会社 All solid state secondary battery
US20110123866A1 (en) * 2009-09-03 2011-05-26 Pan Lawrence S Methods and systems for making electrodes having at least one functional gradient therein and devices resulting therefrom

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1415121A (en) * 1999-10-22 2003-04-30 三洋电机株式会社 Electrode for lithium cell and rechargeable lithium cell

Also Published As

Publication number Publication date
CN103746089A (en) 2014-04-23

Similar Documents

Publication Publication Date Title
CN103746089B (en) A kind of solid lithium battery with gradient-structure and preparation method thereof
US20200335756A1 (en) Solid-state battery separators and methods of fabrication
JP2023011777A (en) Ion-conducting battery containing solid electrolyte material
US9673478B2 (en) Multi-layer coatings for bipolar rechargeable batteries with enhanced terminal voltage
JP5930035B2 (en) All solid state battery and manufacturing method thereof
CN108878775A (en) It is a kind of to mend lithium composite negative pole pole piece and preparation method thereof safely
US10535870B2 (en) Electrical device
WO2015107423A2 (en) Aqueous electrolyte sodium ion secondary battery, and charge/discharge system including same
US20100291444A1 (en) Multilayer coatings for rechargeable batteries
CN111785923A (en) Lithium ion battery anode, preparation method and application thereof, and lithium ion battery
CN111987348B (en) Preparation method of NASICON type solid-state battery
CN111435757B (en) Composite polymer electrolyte, preparation method thereof and lithium battery
US20210050157A1 (en) Hybrid electrode materials for bipolar capacitor-assisted solid-state batteries
WO2020038011A1 (en) Lithium ion battery and preparation method therefor, and electric vehicle
WO2016123471A1 (en) Electrochemical energy storage device
CN109980290B (en) Mixed solid-liquid electrolyte lithium storage battery
WO2020135110A1 (en) Negative active material, battery and apparatus
WO2022057189A1 (en) Solid-state battery, battery module, battery pack, and related device thereof
CN113451586A (en) Electrode plate of secondary battery, secondary battery and preparation method of secondary battery
CN110416630B (en) All-solid-state battery
CN110495035B (en) Lithium ion secondary battery
CN109119635B (en) Battery with a battery cell
WO2013146454A1 (en) Electrode material, all-solid-state lithium secondary battery, and manufacturing method
CN116454202A (en) Sodium ion battery and electric equipment
CN116544352A (en) Sodium ion battery cathode and preparation method thereof, and sodium ion battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20170712

Address after: 317500, Zhejiang Province, Wenling, Taizhou City, the eastern part of the New District incubation base of small and medium enterprises A District, building 9, standard plant floor

Patentee after: Zhejiang long battery technology Co., Ltd.

Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932

Patentee before: Central South University

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20220411

Address after: 317599 Room 606, building 34, Wulong community, Taiping Street, Wenling City, Taizhou City, Zhejiang Province

Patentee after: Wang Haibin

Address before: 317500 1st floor, standard workshop, building 9, area a, SME Incubation Park base, Eastern New District, Wenling City, Taizhou City, Zhejiang Province

Patentee before: ZHEJIANG LONGJIN BATTERY TECHNOLOGY CO.,LTD.

TR01 Transfer of patent right