CN106848390B - A kind of film lithium cell of 3D structure - Google Patents

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

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Publication number
CN106848390B
CN106848390B CN201611102950.0A CN201611102950A CN106848390B CN 106848390 B CN106848390 B CN 106848390B CN 201611102950 A CN201611102950 A CN 201611102950A CN 106848390 B CN106848390 B CN 106848390B
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China
Prior art keywords
anode
silicon substrate
film
cathode
solid electrolyte
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Expired - Fee Related
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CN201611102950.0A
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CN106848390A (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 cells of 3D structure, including silicon substrate, it is respectively plus plate current-collecting body and negative current collector in silicon substrate surface two sides, many regularly arranged micropores are processed on silicon substrate, Li+ diffusion barrier TiN is deposited in micropore, it then is solid electrolyte, LiCoO using silicon as cathode2Battery is made for anode, 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 is all made of multiple-unit cladding lamination electric pile structure, based on flow collection sheet, flow collection sheet and anode, carbon film and diaphragm are successively equipped between cathode, it is cladding dead ring between positive electrode and negative electrode, it will be positive, electrolysis liquid space between cathode and electrolyte is kept apart by coating dead ring, effectively prevent the generation of internal short-circuit between adjacent cell electrode, it ensure that the stability and discharge capacity of battery operating voltage.

Description

A kind of film lithium cell of 3D structure
Technical field
The present invention relates to technical field of lithium batteries, specially a kind of film lithium cell of 3D structure.
Background technique
Electrochmical power source development develops towards the direction of high-energy-density, long-life, high safety always, with the 1990s The development of the invention of lithium ion battery, electrochmical power source has stepped an important step.It deepens continuously in Study on Li-ion batteries same When, people, which begin trying to study, possesses more high-energy-density, more long circulation life, safer battery than lithium ion battery.1983 Year, all solid state inorganic thin film lithium battery is developed in the propositions such as K.Kanehori, theoretically has ratio more higher than lithium ion battery Energy, also safer, then, people have gradually started the research of inorganic full-solid film lithium cell, with TiS2, MoO1.6S1.8 Equal films are cathode, and glassy oxide is developed for all solid-state thin-film lithium battery of electrolyte, but these battery performances It is poor.
Summary of the invention
In view of the above problems, the present invention provides a kind of film lithium cell of 3D structure, using film anode and cathode and Thin film solid state electrolyte, the film morphology of inorganic solid electrolyte make the lower solid electrolyte of ionic conductivity replace liquid electric Solution matter be possibly realized, and anode and cathode film morphology allow to using many charge and discharge volume changes it is biggish anode and Negative electrode material, simultaneously as the film morphology of film lithium cell, makes it be easy to be processed into micron order battery, battery structure letter Single, antidetonation, impact resistance, leakage and pollution problem is not present in handling ease, electrochemically stable, thermostabilization, is easy to minimize and make At film, lamination electric pile structure is coated using multiple-unit, the generation of internal short-circuit phenomenon is reduced, effectively prevents adjacent cell electrode Between internal short-circuit generation, ensure that the stability and discharge capacity of battery operating voltage, can effectively solve in background technique Problem.
To achieve the above object, the invention provides the following technical scheme: a kind of film lithium cell of 3D structure, including silicon substrate Body is respectively plus plate current-collecting body and negative current collector in silicon substrate surface two sides, processes on silicon substrate many regularly arranged Micropore deposits Li+ diffusion barrier TiN in micropore, and then using silicon as cathode, LiPON is solid electrolyte, LiCoO2It is positive Battery is made in pole, 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 are all made of multiple-unit cladding lamination electric pile structure, based on flow collection sheet, flow collection sheet Anode, be successively equipped with carbon film and diaphragm between cathode, be cladding dead ring between positive electrode and negative electrode, by anode and cathode and Electrolysis liquid space between electrolyte is kept apart by coating dead ring.
Preferably, the LiPON dielectric film of the solid electrolyte synthesis optimal proportion is Li2.88PO3.73N0.14, it is logical It crosses in N2The film sputtered under atmosphere, and its chemical property and electrochemical properties are stablized.
Preferably, the packaging protection layer is to form the protection of vibration proof, 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, then rises at 750-850 DEG C Calcining 2-4 hours, obtains the solid lithium battery electrolyte.
Compared with prior art, the beneficial effects of the present invention are: the present invention is using film anode and cathode and thin film solid state Electrolyte, the film morphology of inorganic solid electrolyte become the lower solid electrolyte of ionic conductivity instead of liquid electrolyte May, and the film morphology of anode and cathode allows to using the biggish anode of many charge and discharge volume changes and cathode 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 It being easy, antidetonation, impact resistance, leakage and pollution problem is not present in electrochemically stable, thermostabilization, 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 ensure that the stability and discharge capacity of battery operating voltage.
Detailed description of the invention
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 substrate；2- plus plate current-collecting body；3- negative current collector；4- anode；5- cathode；6- solid electrolyte；7- encapsulation Protective layer；8- flow collection sheet；9- carbon film；10- diaphragm；11- coats dead ring；12- is electrolysed liquid space.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Embodiment:
Fig. 1 and Fig. 2 are please referred to, the present invention provides a kind of technical solution: a kind of film lithium cell of 3D structure, including silicon substrate Body 1 is respectively plus plate current-collecting body 2 and negative current collector 3 in 1 surface two sides of silicon substrate, many rule rows is processed on silicon substrate 1 The micropore of column deposits Li+ diffusion barrier TiN in micropore, and then using silicon as cathode 4, LiPON is solid electrolyte 6, LiCoO2Battery is made for anode 5, and forms packaging protection layer 7, clad anode collector 2, negative current collector on silicon substrate 1 3 and solid electrolyte 6, the plus plate current-collecting body 2, negative current collector 3 are all made of multiple-unit cladding lamination electric pile structure, with collection Based on flow 8, carbon film 9 and diaphragm 10 are successively equipped between flow collection sheet 8 and anode 4, cathode 5, between anode 4 and cathode 5 To coat dead ring 11, anode 4 and the electrolysis liquid space 12 between cathode 5 and electrolyte are kept apart by coating dead ring 11 Come.
The LiPON dielectric film of the solid electrolyte synthesis optimal proportion is Li2.88PO3.73N0.14, it is by N2Gas The film sputtered under atmosphere, and its chemical property and electrochemical properties are stablized；The packaging protection layer is to utilize elastic gel The protective layer of vibration proof, impact is 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, then rises at 750-850 DEG C Calcining 2-4 hours, obtains the solid lithium battery electrolyte.
The present invention using film anode and cathode and thin film solid state electrolyte, the film morphology of inorganic solid electrolyte make from The lower solid electrolyte of electron conductivity is possibly realized instead of liquid electrolyte, and the film morphology of anode and cathode allows to Using the biggish anode of many charge and discharge volume changes and negative electrode material, 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, thermostabilization, antidetonation, impact resistance, no There are leakage and pollution problem, it is easy to minimize and be made film, lamination electric pile structure is coated using multiple-unit, reduces internal short-circuit The generation of phenomenon effectively prevents the generation of internal short-circuit between adjacent cell electrode, ensure that battery operating voltage stability and Discharge capacity.
Solid film lithium battery easy processing be it is micro-, receive battery, and there is many advantages such as specific energy, good cycle, institute It will be the direction of micro cell development with it.As that studies film lithium cell gos deep into, novel electrolyte and anode and it is negative The research and development of pole, all solid-state thin-film lithium battery performance will be promoted further, meanwhile, difficulty of processing and decrease machining cost make it It is possible that replacing existing lithium ion battery, become the final goal of secondary cell development.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (1)

1. a kind of film lithium cell of 3D structure, which is characterized in that be respectively anode in silicon substrate surface two sides including silicon substrate Collector and negative current collector process many regularly arranged micropores on silicon substrate, Li+ diffusion barrier are deposited in micropore TiN, then using silicon as cathode, LiPON is solid electrolyte, LiCoO2Battery is made for anode, and forms envelope on silicon substrate Protective layer is filled, clad anode collector, negative current collector and solid electrolyte, the plus plate current-collecting body, negative current collector are adopted With multiple-unit coat lamination electric pile structure, be successively equipped with based on flow collection sheet, between flow collection sheet and anode carbon film and every Film, is successively equipped with carbon film and diaphragm between flow collection sheet and cathode, be cladding dead ring between positive electrode and negative electrode, by anode with Electrolysis liquid space is kept apart by coating dead ring, cathode is kept apart with electrolysis liquid space by coating dead ring, institute The dielectric film for stating solid electrolyte synthesis optimal proportion is Li2.88PO3.73N0.14, it is by N2Sputtering obtains under atmosphere Film, and its chemical property and electrochemical properties are stablized, the packaging protection layer be using elastic gel around battery shape At vibration proof, the protective layer of impact, the solid electrolyte is by by CH3COOLi、LiPON、La2O3And ZrO2Mixing Grinding, mixture after grinding under an inert atmosphere, first pre-burning 80-120 minutes at 500-580 DEG C, then rise to 750- It is calcined 2-4 hours at 850 DEG C, obtains the solid 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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