CN105529453B - A kind of 3V can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole - Google Patents

A kind of 3V can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole Download PDF

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Publication number
CN105529453B
CN105529453B CN201510818761.2A CN201510818761A CN105529453B CN 105529453 B CN105529453 B CN 105529453B CN 201510818761 A CN201510818761 A CN 201510818761A CN 105529453 B CN105529453 B CN 105529453B
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lithium
negative pole
aluminium alloy
aluminium
alloy negative
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CN105529453A (en
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叶丽光
郝德利
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TIANJIN HEWEI TECHNOLOGY CO LTD
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TIANJIN HEWEI 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Abstract

It is an object of the invention to provide the preparation method that a kind of 3V can fill button lithium battery lithium-aluminium alloy negative pole, this method has the characteristics of technique is simple, speed is fast, performance is good, suitable automatic mass production.The present invention is to be realized by the following technical programs, and a kind of 3V can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole, and its preparation process is：The aluminium sheet of purity more than 99% is processed into a disk, a diameter of 0.3 ~ 0.5mm through hole is processed on disk, according to radial distribution（Fig. 1）Oil removing and water removal drying are carried out to aluminium flake, in dry environment of the relative humidity less than 1%, by lithium piece together with aluminium flake cold rolling, kept for more than 10 seconds, obtain lithium-aluminium alloy negative pole, for the mol ratio of described metal lithium sheet and aluminium flake between 0.8 ~ 1.0, the described through hole gross area accounts for the 48% ~ 62% of the aluminium sheet circle gross area.It is an advantage of the invention that the preparation method that a kind of 3V can fill button lithium battery lithium-aluminium alloy negative pole is adapted to the extensive quick production of industrialization, while there is advanced performance.

Description

A kind of 3V can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole
Technical field
The invention discloses the preparation method that a kind of 3V can fill button lithium battery lithium-aluminium alloy negative pole, belongs to electrochmical power source storage Can technical field.
Background technology
Due to the popularization and fast development of electronic product, it is increasing to fill lithium/manganese dioxide button cell demand, and Existing to fill in lithium/manganese dioxide battery production process, the manufacturing speed of lithium-aluminium alloy negative pole is very low, limits the big of yield Amplitude is lifted.
The negative pole of existing lithium-aluminium alloy is typically using method disclosed in similar CN87100735, i.e., at normal temperatures with rolling altogether Technique prepares lithium-aluminium alloy coating：In environment of the relative humidity less than 1%, by commercially available fine aluminium or aluminium alloy without lithium with Lithium metal rolls together, and pressurization forms lithium-aluminium alloy coating on aluminum surfaces after being kept for 24 hours.
The invention discloses the preparation method that a kind of 3V can fill button lithium battery lithium-aluminium alloy negative pole, can quickly prepare Lithium-aluminium alloy negative pole, it is adapted to the large batch of production of automation.
The content of the invention
It is an object of the invention to provide the preparation method that a kind of 3V can fill button lithium battery lithium-aluminium alloy negative pole, this method With technique is simple, speed is fast, performance is good, is adapted to the characteristics of automatic mass production.
The present invention is to be realized by the following technical programs, and a kind of 3V can fill button lithium battery lithium-aluminium alloy negative pole Preparation method, its preparation process are：
The aluminium sheet of purity more than 99% is processed into a disk, a diameter of 0.3~0.5mm through hole is processed on disk, According to radial distribution (Fig. 1), oil removing and water removal drying are carried out to aluminium flake, will in dry environment of the relative humidity less than 1% Lithium piece is kept for more than 10 seconds together with aluminium flake cold rolling, obtains lithium-aluminium alloy negative pole, and described metal lithium sheet and aluminium flake rub For that ratio between 0.8~1.0, the described through hole gross area accounts for the 48%~62% of the aluminium sheet circle gross area.
It is an advantage of the invention that the preparation method that a kind of 3V can fill button lithium battery lithium-aluminium alloy negative pole is adapted to industrialization big Scale quickly produces, while has advanced performance.It is cold in lithium piece and aluminium flake due to the through hole of radial distribution on aluminium flake be present During rolling together, concentric circular direction flow behavior is often presented in lithium metal, and lithium metal can be preferentially full of in aperture, and These lithium metals being filled in aperture may proceed to spread into metallic aluminium, so as to which aluminium/lithium metal diffusion interface is extended to Three-dimensional, contact area is expanded, shorten time and the distance of diffusion, the lithium-aluminium alloy negative pole size of formation is basically unchanged, can To be immediately available for battery assembling, the purpose of quick production is reached, has been improved than method unit production capacity disclosed in CN87100735 More than 1000 times.On the other hand, direction diffusion of the lithium metal inserted in aperture along parallel metal aluminium sheet is entered, and makes elemental lithium Being more evenly distributed in aluminium flake, therefore cycle performance is more preferable.Circulated under 0.1C, 72% charging and discharging depth, when its capacity Less than initial value 72% when, cycle-index has reached 80 times.
Brief description of the drawings
Fig. 1 is the top view that aluminium sheet is processed into disk.8 rays, two phases are uniformly distributed on disk centered on the center of circle Angle between adjacent ray is 45 degree, and spacing is uniformly dispersed with diameter identical through hole on every ray.
Embodiment
Embodiment 1
(1) by ML1220 negative electrode casings, inside bottom welds the nickel screen that one piece of a diameter of 3mm thickness is 0.2mm, then removes Oil, after cleaning up, in 105 DEG C of forced air dryings 4 hours；
(2) purity 99%, thickness 0.52mm aluminium sheet on, go out diameter 9mm disks, gone out on disk a diameter of The through hole of 0.5mm radial distribution 180, then after oil removing, cleaning, in 105 DEG C of forced air dryings 2 hours；
(3) aluminium flake handled well is put into negative electrode casing, with 0.5MPa power plastics pressure head jewelling on pneumatic press Piece, 3 seconds, aluminium flake is fixed on inside negative electrode casing.
(4) in the drying room that relative humidity is 0.9%, Battery grade lithium metal piece 10mg is placed among aluminium flake, with punching Head applies 5MPa pressure, removes pressure after being kept for 10 seconds, button lithium battery lithium-aluminium alloy negative pole can be filled by obtaining 3V.
(5) PP barrier films are put on negative pole, add 0.2g electrolyte 1M LiPF6/ (EC+DMC+PC), then puts on barrier film Low pressure lithium manganate anode slice, anode cover is finally covered, seal, obtain ML1220 button cells.
(6) 0.1C charge-discharge tests are carried out to this battery, charging upper limit 3.25V, electric discharge lower limit is 2.0V, test data It is 3.0V to show its operating voltage.According to 72%DOD, 0.1C charge-discharge test life-spans, cycle life is 82 times.
Embodiment 2
(1) by ML1220 negative electrode casings, inside bottom welds the nickel screen that one piece of a diameter of 3mm thickness is 0.2mm, then removes Oil, after cleaning up, in 105 DEG C of forced air dryings 4 hours；
(2) on purity 99%, thickness 0.5mm aluminium sheets, diameter 9mm disks is gone out, a diameter of 0.3mm is gone out on disk Radial distribution through hole 510, then after oil removing, cleaning, in 105 DEG C of forced air dryings 2 hours；
(3) aluminium flake handled well is put into negative electrode casing, with 0.3MPa power plastics pressure head jewelling on pneumatic press Piece, 3 seconds, aluminium flake is fixed on inside negative electrode casing.
(4) in the drying room that relative humidity is 0.9%, Battery grade lithium metal piece 10mg is placed among aluminium flake, with punching Head (having annular groove on punch contact surface) applies 5MPa pressure, and pressure is removed after being kept for 10 seconds, and button lithium electricity can be filled by obtaining 3V Pond lithium-aluminium alloy negative pole.
(5) PP barrier films are put on negative pole, add 0.2g electrolyte 1M LiPF6/ (EC+DMC+PC), then puts on barrier film Low pressure lithium manganate anode slice, anode cover is finally covered, seal, obtain ML1220 button cells.
(6) 0.1C charge-discharge tests are carried out to this battery, charging upper limit 3.25V, electric discharge lower limit is 2.0V, test data It is 3.0V to show its operating voltage.According to 72%DOD, 0.1C charge-discharge test life-spans, cycle life is 81 times.
Embodiment 3
(1) by ML1220 negative electrode casings, inside bottom welds the nickel screen that one piece of a diameter of 3mm thickness is 0.2mm, then removes Oil, after cleaning up, in 105 DEG C of forced air dryings 4 hours；
(2) on purity 99%, thickness 0.46mm aluminium sheets, diameter 9mm disks is gone out, are gone out on disk a diameter of The through hole of 0.3mm radial distribution 460, then after oil removing, cleaning, in 105 DEG C of forced air dryings 2 hours；
(3) aluminium flake handled well is put into negative electrode casing, with 0.3MPa power plastics pressure head jewelling on pneumatic press Piece, 3 seconds, aluminium flake is fixed on inside negative electrode casing.
(4) in the drying room that relative humidity is 0.9%, Battery grade lithium metal piece 8mg is placed among aluminium flake, uses drift (having annular groove on punch contact surface) applies 5MPa pressure, removes pressure after being kept for 10 seconds, button lithium battery can be filled by obtaining 3V Lithium-aluminium alloy negative pole.
(5) PP barrier films are put on negative pole, add 0.2g electrolyte 1M LiPF6/ (EC+DMC+PC), then puts on barrier film Low pressure lithium manganate anode slice, anode cover is finally covered, seal, obtain ML1220 button cells.
(6) 0.1C charge-discharge tests are carried out to this battery, charging upper limit 3.25V, electric discharge lower limit is 2.0V, test data It is 3.0V to show its operating voltage.According to 72%DOD, 0.1C charge-discharge test life-spans, cycle life is 85 times.

Claims (3)

1. a kind of 3V can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole, it is characterised in that：The aluminium sheet of purity more than 99% A disk is processed into, a diameter of 0.3 ~ 0.5mm through hole is processed on disk, according to radial distribution, disk is removed Oil and water removal drying, relative humidity less than 1% dry environment in, by lithium piece with disk cold rolling together with, holding 10 seconds with On, button lithium battery lithium-aluminium alloy negative pole can be filled by obtaining 3V.
2. a kind of 3V according to claim 1 can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole, its feature exists In：Described cold rolling lithium piece together and the mol ratio of disk are between 0.8 ~ 1.0.
3. a kind of 3V according to claim 1 can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole, its feature exists In：The gross area of described through hole accounts for the 48% ~ 62% of the disk gross area.
CN201510818761.2A 2015-11-22 2015-11-22 A kind of 3V can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole Active CN105529453B (en)

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CN107565088B (en) * 2017-07-13 2021-01-08 天津理工大学 Preparation method of negative electrode of lithium metal secondary battery
US20210104774A1 (en) * 2018-02-01 2021-04-08 Honda Motor Co., Ltd. Solid-state battery and method for producing solid-state battery
CN110364686B (en) * 2019-07-15 2023-01-20 湖北锂诺新能源科技有限公司 Method for manufacturing negative electrode of rechargeable button lithium-manganese battery
CN114361401A (en) * 2020-10-13 2022-04-15 宜昌力佳科技有限公司 Method for manufacturing button primary battery lithium-aluminum alloy cathode
CN114421069A (en) * 2020-10-13 2022-04-29 宜昌力佳科技有限公司 Manufacturing method of wide-temperature button cell with lithium-aluminum alloy as negative electrode

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CN87100735A (en) * 1986-02-19 1987-09-09 塞格杜尔·皮奇尼铝加工公司 With hot common roll process is the method for lithium-containing aluminum alloy coating
CN102127660A (en) * 2011-02-28 2011-07-20 天津赫维科技有限公司 Lithium aluminum alloy for secondary lithium battery and manufacturing method thereof
JP2011249286A (en) * 2010-05-31 2011-12-08 Sumitomo Electric Ind Ltd Alloy negative electrode for lithium battery and manufacturing method thereof, and lithium battery
CN102610848A (en) * 2011-01-21 2012-07-25 天津赫维科技有限公司 Chargeable 3V button-type lithium battery
CN104060141A (en) * 2014-07-14 2014-09-24 四川天齐锂业股份有限公司 Vacuum synthesis method of lithium-aluminum alloy
CN104701495A (en) * 2013-12-05 2015-06-10 天津赫维科技有限公司 Production method of lithium-aluminum alloy negative electrode for button battery

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Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
CN87100735A (en) * 1986-02-19 1987-09-09 塞格杜尔·皮奇尼铝加工公司 With hot common roll process is the method for lithium-containing aluminum alloy coating
JP2011249286A (en) * 2010-05-31 2011-12-08 Sumitomo Electric Ind Ltd Alloy negative electrode for lithium battery and manufacturing method thereof, and lithium battery
CN102610848A (en) * 2011-01-21 2012-07-25 天津赫维科技有限公司 Chargeable 3V button-type lithium battery
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