CN106848390A - A kind of film lithium cell of 3D structures - Google Patents

A kind of film lithium cell of 3D structures Download PDF

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Publication number
CN106848390A
CN106848390A CN201611102950.0A CN201611102950A CN106848390A CN 106848390 A CN106848390 A CN 106848390A CN 201611102950 A CN201611102950 A CN 201611102950A CN 106848390 A CN106848390 A CN 106848390A
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China
Prior art keywords
film
positive pole
negative
silicon substrate
pole
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CN201611102950.0A
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CN106848390B (en
Inventor
陈辉
张健康
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DONGGUAN LVJUN E-BIKE TECHNOLOGY Co Ltd
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DONGGUAN LVJUN E-BIKE TECHNOLOGY 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • 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 discloses a kind of film lithium cell of 3D structures, including silicon substrate, plus plate current-collecting body and negative current collector are respectively in silicon substrate surface both sides, many regularly arranged micropores are processed on silicon substrate, Li+ diffusion barriers TiN is deposited in micropore, then it is solid electrolyte, LiCoO with silicon as negative pole2For positive pole is made battery, and packaging protection layer is formed on silicon substrate, clad anode collector, negative current collector and solid electrolyte, the plus plate current-collecting body, negative current collector coats lamination electric pile structure using multiple-unit, based on flow collection sheet, flow collection sheet and positive pole, carbon film and barrier film are equipped between negative pole successively, it is coated insulation ring between positive pole and negative pole, by positive pole, electrolysis liquid space between negative pole and electrolyte is kept apart by coated insulation ring, effectively prevent the generation of internal short-circuit between adjacent cell electrode, ensure that the stability and discharge capacity of battery operating voltage.

Description

A kind of film lithium cell of 3D structures
Technical field
The present invention relates to technical field of lithium batteries, specially a kind of film lithium cell of 3D structures.
Background technology
The direction that electrochmical power source develops always towards high-energy-density, long-life, high safety is developed, with the nineties in 20th century The invention of lithium ion battery, the development of electrochmical power source has stepped an important step.Study on Li-ion batteries deepen continuously it is same When, people begin attempt to research and possess more high-energy-density, more long circulation life, safer battery than lithium ion battery.1983 Year, K.Kanehori etc. proposes all solid state inorganic thin film lithium battery of exploitation, and it has the ratio higher than lithium ion battery in theory Energy, also safer, then, people have gradually started the research of inorganic full-solid film lithium cell, with TiS2, MoO1.6S1.8 It is negative electrode Deng film, glassy oxide is developed for all solid-state thin-film lithium battery of electrolyte, but these battery performances It is poor.
The content of the invention
For problem above, the invention provides a kind of film lithium cell of 3D structures, using film positive pole and negative pole and Thin film solid state electrolyte, the solid electrolyte that the film morphology of inorganic solid electrolyte makes ionic conductivity relatively low replaces liquid electric Solution matter is possibly realized, and the film morphology of positive pole and negative pole allows it using the larger positive pole of many discharge and recharge Volume Changes and Negative material, simultaneously as the film morphology of film lithium cell, makes it be easy to be processed into micron order battery, battery structure letter It is single, handling ease, electrochemically stable, thermally-stabilised, antidetonation, impact resistance, in the absence of leakage and pollution problem, it is easy to miniaturization and make Into film, lamination electric pile structure is coated using multiple-unit, reduce the generation of internal short-circuit phenomenon, effectively prevent adjacent cell electrode Between internal short-circuit generation, it is ensured that the stability and discharge capacity of battery operating voltage, in can effectively solving background technology Problem.
To achieve the above object, the present invention provides following technical scheme：A kind of film lithium cell of 3D structures, including silicon substrate Body, plus plate current-collecting body and negative current collector are respectively in silicon substrate surface both sides, process many regularly arranged on silicon substrate Micropore, deposits Li+ diffusion barrier TiN in micropore, and then with silicon as negative pole, LiPON is solid electrolyte, LiCoO2For just Pole is made battery, and packaging protection layer is formed on silicon substrate, clad anode collector, negative current collector and solid electrolyte, The plus plate current-collecting body, negative current collector coat lamination electric pile structure, based on flow collection sheet, flow collection sheet using multiple-unit Be equipped with carbon film and barrier film successively between positive pole, negative pole, be coated insulation ring between positive pole and negative pole, by positive pole and negative pole and Electrolysis liquid space between electrolyte is kept apart by coated insulation ring.
Preferably, the LiPON dielectric films of the solid electrolyte synthesis optimal proportion are Li2.88PO3.73N0.14, it is logical Cross in N2The film for obtaining, and its chemical property and electrochemical properties stabilization are sputtered under atmosphere.
Preferably, the packaging protection layer is to form vibration proof, the protection of impact around battery using elastic gel Layer.
Preferably, the solid electrolyte is by by CH3COOLi、LiPON、La2O3And ZrO2Mixed grinding, Mixture after grinding under an inert atmosphere, first pre-burning 80-120 minutes at 500-580 DEG C, is then risen at 750-850 DEG C Calcining 2-4 hours, obtains the solid lithium battery electrolyte.
Compared with prior art, the beneficial effects of the invention are as follows：The present invention uses film positive pole and negative pole and thin film solid state Electrolyte, the solid electrolyte that the film morphology of inorganic solid electrolyte makes ionic conductivity relatively low turns into instead of liquid electrolyte May, and the film morphology of positive pole and negative pole allows it using many discharge and recharge Volume Changes larger positive pole and negative pole material Material, simultaneously as the film morphology of film lithium cell, makes it be easy to be processed into micron order battery, battery structure is simple, processing Easily, electrochemically stable, thermally-stabilised, antidetonation, impact resistance, in the absence of leakage and pollution problem, it is easy to minimize and be made film, Lamination electric pile structure is coated using multiple-unit, the generation of internal short-circuit phenomenon is reduced, effectively prevents adjacent cell electrode interior short The generation on road, it is ensured that the stability and discharge capacity of battery operating voltage.
Brief description of the drawings
Fig. 1 is schematic structural view of the invention.
Fig. 2 is that multiple-unit of the present invention coats lamination electric pile structure schematic diagram.
1- silicon substrates；2- plus plate current-collecting bodies；3- negative current collectors；4- positive poles；5- negative poles；6- solid electrolytes；7- is encapsulated Protective layer；8- flow collection sheets；9- carbon films；10- barrier films；11- coated insulation rings；12- is electrolysed liquid space.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made Embodiment, belongs to the scope of protection of the invention.
Embodiment：
Fig. 1 and Fig. 2 is referred to, the present invention provides a kind of technical scheme：A kind of film lithium cell of 3D structures, including silicon substrate 1, Plus plate current-collecting body 2 and negative current collector 3 are respectively in the surface both sides of silicon substrate 1, process many regularly arranged on silicon substrate 1 Micropore, deposits Li+ diffusion barrier TiN in micropore, is then negative pole 4 with silicon, and LiPON is solid electrolyte 6, LiCoO2For Positive pole 5 is made battery, and packaging protection layer 7, clad anode collector 2, negative current collector 3 and solid-state are formed on silicon substrate 1 Electrolyte 6, the plus plate current-collecting body 2, negative current collector 3 coat lamination electric pile structure using multiple-unit, are with flow collection sheet 8 Main body, is equipped with carbon film 9 and barrier film 10 successively between flow collection sheet 8 and positive pole 4, negative pole 5, for cladding is exhausted between positive pole 4 and negative pole 5 Edge ring 11, the electrolysis liquid space 12 between positive pole 4 and negative pole 5 and electrolyte is kept apart by coated insulation ring 11.
The LiPON dielectric films of the solid electrolyte synthesis optimal proportion are Li2.88PO3.73N0.14, it is by N2Gas The film for obtaining, and its chemical property and electrochemical properties stabilization are sputtered under atmosphere；The packaging protection layer is to utilize elastic gel Vibration proof, the protective layer of impact are formed around battery.
Preferably, the solid electrolyte is by by CH3COOLi、LiPON、La2O3And ZrO2Mixed grinding, Mixture after grinding under an inert atmosphere, first pre-burning 80-120 minutes at 500-580 DEG C, is then risen at 750-850 DEG C Calcining 2-4 hours, obtains the solid lithium battery electrolyte.
The present invention uses film positive pole and negative pole and thin film solid state electrolyte, the film morphology of inorganic solid electrolyte make from The relatively low solid electrolyte of electron conductivity is possibly realized instead of liquid electrolyte, and the film morphology of positive pole and negative pole makes it can be with Using positive pole and negative material that many discharge and recharge Volume Changes are larger, simultaneously as the film morphology of film lithium cell, makes it It is easy to be processed into micron order battery, battery structure is simple, handling ease, electrochemically stable, thermally-stabilised, antidetonation, impact resistance, no There is leakage and pollution problem, it is easy to minimize and be made film, lamination electric pile structure is coated using multiple-unit, reduce internal short-circuit The generation of phenomenon, effectively prevents the generation of internal short-circuit between adjacent cell electrode, it is ensured that the stability of battery operating voltage and Discharge capacity.
Solid film lithium battery easy processing for it is micro-, battery is received, and with many advantages such as specific energy, good cycle, institute Will be the direction that micro cell develops with it.With going deep into for studying film lithium cell, new electrolyte and positive pole and negative The research and development of pole, all solid-state thin-film lithium battery performance will be lifted further, meanwhile, its difficulty of processing and decrease machining cost make it It is possible to replace existing lithium ion battery, the final goal as secondary cell development.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.

Claims (4)

1. a kind of film lithium cell of 3D structures, it is characterised in that including silicon substrate, positive pole is respectively in silicon substrate surface both sides Collector and negative current collector, process many regularly arranged micropores on silicon substrate, and Li+ diffusion barriers are deposited in micropore TiN, is solid electrolyte, LiCoO then with silicon as negative pole2For positive pole is made battery, and packaging protection is formed on silicon substrate Layer, clad anode collector, negative current collector and solid electrolyte, the plus plate current-collecting body, negative current collector are using more single Unit cladding lamination electric pile structure, be equipped with successively based on flow collection sheet, between flow collection sheet and positive pole, negative pole carbon film and every Film, is coated insulation ring between positive pole and negative pole, and the electrolysis liquid space between positive pole, negative pole and electrolyte is passed through into coated insulation Ring is kept apart.
2. a kind of film lithium cell of 3D structures according to claim 1, it is characterised in that the solid electrolyte synthesis The dielectric film of optimal proportion is Li2.88PO3.73N0.14, it is by N2The film for obtaining, and its chemical property are sputtered under atmosphere With electrochemical properties stabilization.
3. the film lithium cell of a kind of 3D structures according to claim 1, it is characterised in that the packaging protection layer is profit Vibration proof, the protective layer of impact are formed around battery with elastic gel.
4. the film lithium cell of a kind of 3D structures according to claim 1, it is characterised in that the solid electrolyte is logical Cross CH3COOLi、LiPON、La2O3And ZrO2Mixed grinding, mixture after grinding under an inert atmosphere, first exists Pre-burning 80-120 minutes at 500-580 DEG C, calcined 2-4 hours at then rising to 750-850 DEG C, obtain all solid lithium electricity Pond electrolyte.
CN201611102950.0A 2016-12-05 2016-12-05 A kind of film lithium cell of 3D structure Expired - Fee Related CN106848390B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1945881A (en) * 2006-11-02 2007-04-11 复旦大学 Full solid thin film lithium battery and its producing method
CN101771168A (en) * 2010-02-11 2010-07-07 厦门大学 Method for preparing miniature lithium battery
CN104134816A (en) * 2014-08-05 2014-11-05 厦门大学 Three-dimensional all-solid-state mini thin-film lithium battery with inverted pyramid array structure
CN204947000U (en) * 2015-09-20 2016-01-06 东莞市格能电子科技有限公司 A kind of coated lamination pile of multiple unit of reserve type lamination lithium battery flow collection sheet
CN105900212A (en) * 2014-01-24 2016-08-24 应用材料公司 Deposition of solid state electrolyte on electrode layers in electrochemical devices
CN106058305A (en) * 2016-08-12 2016-10-26 合肥国轩高科动力能源有限公司 Method for in-situ preparation of minisized all-solid-state thin-film lithium-ion battery by using PLD

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1945881A (en) * 2006-11-02 2007-04-11 复旦大学 Full solid thin film lithium battery and its producing method
CN101771168A (en) * 2010-02-11 2010-07-07 厦门大学 Method for preparing miniature lithium battery
CN105900212A (en) * 2014-01-24 2016-08-24 应用材料公司 Deposition of solid state electrolyte on electrode layers in electrochemical devices
CN104134816A (en) * 2014-08-05 2014-11-05 厦门大学 Three-dimensional all-solid-state mini thin-film lithium battery with inverted pyramid array structure
CN204947000U (en) * 2015-09-20 2016-01-06 东莞市格能电子科技有限公司 A kind of coated lamination pile of multiple unit of reserve type lamination lithium battery flow collection sheet
CN106058305A (en) * 2016-08-12 2016-10-26 合肥国轩高科动力能源有限公司 Method for in-situ preparation of minisized all-solid-state thin-film lithium-ion battery by using PLD

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