CN109920980A - A kind of preparation method of the lithium battery lithium anode of surface coating decoration - Google Patents

A kind of preparation method of the lithium battery lithium anode of surface coating decoration Download PDF

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Publication number
CN109920980A
CN109920980A CN201910118942.2A CN201910118942A CN109920980A CN 109920980 A CN109920980 A CN 109920980A CN 201910118942 A CN201910118942 A CN 201910118942A CN 109920980 A CN109920980 A CN 109920980A
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Prior art keywords
lithium
preparation
solid electrolyte
surface coating
coating decoration
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刘争
付兴杰
徐晓丹
孙宏阳
张业龙
彭章泉
曾庆光
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Wuyi University
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Wuyi University
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    • 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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Abstract

The present invention relates to a kind of preparation methods of the lithium battery lithium anode of surface coating decoration, and lithium metal plate is put into closed anti-container, in argon atmosphere environment, are passed through the nitrogen reaction regular hour, obtain lithium metal plate after surface modification；Solid electrolyte ceramic wafer is subjected to surface polishing processing；Encapsulation process is carried out after together with lithium metal plate after surface modification is fitted closely with solid electrolyte ceramic wafer.The present invention has preferable repeatability, can preferably reduce interface resistance, interface resistance can be stablized in 0-20 Ω cm2, 34-100 Ω cm compared with the existing technology2, can fundamentally solve the problems, such as interface resistance；Preparation process is simple, easily controls, the lithium metal battery lithium an- ode can volume production handled on lithium surface so that the substance of growth in situ and the associativity of lithium are especially strong, further improve the reliability of product and woth no need to large-scale deposition apparatus.

Description

A kind of preparation method of the lithium battery lithium anode of surface coating decoration
Technical field
The present invention relates to battery metal cathode of lithium processing technology field, the lithium battery gold of especially a kind of surface coating decoration Belong to the preparation method of cathode of lithium.
Background technique
Lithium ion battery is a kind of novel battery to grow up on the basis of lithium battery, relies primarily on lithium ion in anode Between cathode it is mobile come work, chemical property depends primarily on electrode material, the lithium ion battery of liquid electrolyte, as Energy storage device is applied to the every aspect of life by everybody, but because of the bottleneck of its energy density and its safety problem, so that greatly Family goes to study various novel batteries one after another, including novel batteries such as lithium metal battery, lithium-sulfur cell and lithium-air batteries, The above battery also has respective problem, if lithium metal battery is easy to produce Li dendrite, will cause very serious safety problem, lithium- Sulphur battery, sulfur electrode can be dissolved in liquid electrolyte, influence service life and the safety of battery, lithium-air battery is then because of its cyclic process The super oxygen root of middle generation can occur side reaction with organic electrolyte, cause the consumption of electrolyte, influence the service life of battery.
For the technical problem more than solving, liquid electrolyte can be substituted using solid electrolyte, because of solid state electrolysis The intensity of matter is high, can the generation of effectively dendrite inhibition will not dissolve sulphur cathode, and because it is compared with liquid in lithium-sulfur cell The more stable property of state electrolyte can also bring more excellent performance in lithium-oxygen battery to battery.But in solid-state electricity In the contact interface of Xie Zhiyu electrode, very big interface resistance is generated, in general inorganic solid electrolyte, be with LLZTO Example, can generate 10 in the contact interface of untreated solid electrolyte and cathode of lithium2、103、104The interface of the even higher order of magnitude Resistance (unit: Ω cm2), therefore, hindering solid electrolyte cannot use on a large scale.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation of the lithium battery lithium anode of surface coating decoration Method.
The technical solution of the present invention is as follows: a kind of preparation method of the lithium battery lithium anode of surface coating decoration, including Following steps:
S1), the lithium metal plate of clean light is put into closed anti-container, in argon atmosphere environment, it is anti-is passed through nitrogen The regular hour is answered, the boundary material of one layer of nanoscale golden yellow is generated in lithium metal plate surface, obtains after surface modification Lithium metal plate；
S2), solid electrolyte ceramic wafer is subjected to surface polishing processing, removes impurity；
S3), by the lithium metal plate and step S2 in step S1) after surface modification) in go deimpurity solid electrolyte to make pottery Porcelain plate fits closely carries out encapsulation process afterwards together.
Further, step S1) in, the concentration of the argon gas is 99%, and the concentration of the nitrogen is 1%.
Further, step S1) in, the nitrogen may be oxygen or ammonia or can by heating method processing With the liquefied gas of volatilization.
Further, step S1) in, the boundary material with a thickness of 1-100 μm.
Further, step S1) in, the golden yellow boundary material is nitrogen oxide.
Further, step S2) in, the solid electrolyte ceramic wafer is Garnet-type solid electrolyte (GARNET) or including Li6.4La3Zr1.4Ta0.6O12(LLZTO)、Li6.3La3Zr1.65W0.35O12(LLZO) different elements proportion And the LLZTO Garnet-type solid electrolyte of doping.
Further, step S3) in lithium an- ode | the unit-area impedance of solid electrolyte be 1.3419 Ω cm2, interface resistance is 0-20 Ω cm2。
Further, the liquid gas is one of vapor, acetone steam, methanol steam or several mixed It closes.
Further, contact of the golden yellow boundary material as lithium metal plate and solid electrolyte ceramic wafer Layer, to increase the tightness of the combination of lithium metal and solid electrolyte.
The invention has the benefit that
1, compared with prior art, the present invention has preferable repeatability, can preferably reduce interface resistance, interface Resistance can be stablized in 0-20 Ω cm2, 34-100 Ω cm compared with the existing technology2, can fundamentally solve interface resistance Problem；
2, preparation process is simple, easily controls, it is only necessary to by lithium metal under argon atmosphere environment, progress is reacted with nitrogen Surface modification；
3, the lithium an- ode after lithium metal battery modification can volume production, and woth no need to large-scale deposition apparatus, moreover, It is handled on lithium surface so that the substance of growth in situ and the associativity of lithium are especially strong, further improves the reliable of product Property.
Detailed description of the invention
Fig. 1 is the schematic diagram of lithium electricity lithium an- ode prepared by the present invention；
Fig. 2 is lithium battery lithium anode in the prior art | the impedance spectrum of solid electrolyte；
Fig. 3 is lithium battery lithium anode of the present invention | the impedance spectrum of solid electrolyte；
In figure, 1- lithium metal plate, 2- boundary material, 3- solid electrolyte.
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing:
As shown in Figure 1, the present embodiment provides a kind of preparation method of the lithium battery lithium anode of surface coating decoration, packet Include following steps:
S1), the lithium metal plate of clean light is put into closed anti-container, the argon atmosphere environment for being 99% in concentration It is interior, it is passed through for 1% nitrogen reaction regular hour, generates the golden yellow boundary material of one layer of 1 μ m-thick in lithium metal plate surface Nitrogen oxide obtains lithium metal plate after surface modification；
S2), Garnet-type solid electrolyte (GARNET) is subjected to surface polishing processing, removes impurity；
S3), by the lithium metal plate and step S2 in step S1) after surface modification) in remove deimpurity Garnet-type solid Electrolyte (GARNET) fits closely carries out encapsulation process afterwards together；The lithium anode | the resistance of solid electrolyte unit area Resist for 1.3419 Ω cm2。
As shown in Figures 2 and 3, in ac impedance spectroscopy, there is the resistance close to 60 Ω unrelated with interface, including outer Circuitous resistance and bulk resistance (Bulk resistance, Grain Boundary resistance etc.), it may be assumed that
Interface impedance ≈ [all-in resistance-(external resistance+bulk resistance)] × solid electrolyte/lithium metal interfacial area；
All-in resistance: X-axis intercept (64.26 Ω)；
External resistance+bulk resistance: about 60 Ω；
Solid electrolyte/lithium metal interfacial area: because cross-sectional dimension is 4.5mm, so area is about 0.63cm2
Obtain interface impedance=64.26-60=2.6838 Ω；
Since, there are two lithium solid electrolyte interface, uniform units are Ω cm in a Symmetrical cells2Later: Unit-area impedance=1.3419 Ω cm2, it is believed that completely eliminate the influence of interface resistance.
The above embodiments and description only illustrate the principle of the present invention and most preferred embodiment, is not departing from this Under the premise of spirit and range, various changes and improvements may be made to the invention, these changes and improvements both fall within requirement and protect In the scope of the invention of shield.

Claims (9)

1. a kind of preparation method of the lithium battery lithium anode of surface coating decoration, which comprises the following steps:
S1), the lithium metal plate of clean light is put into closed anti-container, in argon atmosphere environment, is passed through nitrogen reaction one The fixed time generates the boundary material of one layer of nanoscale golden yellow in lithium metal plate surface, obtains lithium gold after surface modification Belong to plate；
S2), solid electrolyte ceramic wafer is subjected to surface polishing processing, removes impurity；
S3), by the lithium metal plate and step S2 in step S1) after surface modification) in remove deimpurity solid electrolyte ceramic wafer It fits closely and carries out encapsulation process afterwards together.
2. a kind of preparation method of the lithium battery lithium anode of surface coating decoration according to claim 1, feature It is: step S1) in, the concentration of the argon gas is 99%, and the concentration of the nitrogen is 1%.
3. a kind of preparation method of the lithium battery lithium anode of surface coating decoration according to claim 1, feature It is: step S1) in, the nitrogen may be oxygen or ammonia or handle the liquid that can be volatilized by heating method Gas.
4. a kind of preparation method of the lithium battery lithium anode of surface coating decoration according to claim 1, feature Be: step S1) in, the boundary material with a thickness of 1-100 μm.
5. a kind of preparation method of the lithium battery lithium anode of surface coating decoration according to claim 1, feature It is: step S1) in, the golden yellow boundary material is nitrogen oxide.
6. a kind of preparation method of the lithium battery lithium anode of surface coating decoration according to claim 1, feature Be: step S2) in, the solid electrolyte ceramic wafer be Garnet-type solid electrolyte (GARNET) or including Li6.4La3Zr1.4Ta0.6O12(LLZTO)、Li6.3La3Zr1.65W0.35O12(LLZO) different elements match the LLZTO stone when adulterated Garnet type solid electrolyte.
7. a kind of preparation method of the lithium battery lithium anode of surface coating decoration according to claim 1, feature Be: step S3) in lithium anode interface resistance be 0-20 Ω cm2, unit-area impedance is 1.3419 Ω cm2。
8. a kind of preparation method of the lithium battery lithium anode of surface coating decoration according to claim 3, feature Be: the liquid gas is one of vapor, acetone steam, methanol steam or several mixing.
9. a kind of preparation method of the lithium battery lithium anode of surface coating decoration according to claim 1, feature It is: contact layer of the golden yellow boundary material as lithium metal plate and solid electrolyte ceramic wafer, to increase metal The tightness of the combination of lithium and solid electrolyte.
CN201910118942.2A 2019-02-18 2019-02-18 A kind of preparation method of the lithium battery lithium anode of surface coating decoration Withdrawn CN109920980A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111224066A (en) * 2020-02-11 2020-06-02 五邑大学 Method for regulating interface between solid electrolyte and metal lithium cathode
CN111370627A (en) * 2020-03-27 2020-07-03 中国人民解放军军事科学院防化研究院 Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm
CN111509195A (en) * 2020-05-07 2020-08-07 武汉理工大学 Surface modification method for metal lithium cathode in all-solid-state lithium battery
US11605836B2 (en) 2020-03-10 2023-03-14 Corning Incorporated Li/garnet electrolyte interface with low interfacial resistance

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111224066A (en) * 2020-02-11 2020-06-02 五邑大学 Method for regulating interface between solid electrolyte and metal lithium cathode
WO2021159595A1 (en) * 2020-02-11 2021-08-19 五邑大学 Method for controlling interface between solid-state electrolyte and metallic lithium negative electrode
US11605836B2 (en) 2020-03-10 2023-03-14 Corning Incorporated Li/garnet electrolyte interface with low interfacial resistance
CN111370627A (en) * 2020-03-27 2020-07-03 中国人民解放军军事科学院防化研究院 Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm
CN111509195A (en) * 2020-05-07 2020-08-07 武汉理工大学 Surface modification method for metal lithium cathode in all-solid-state lithium battery

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