CN105552348B - 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
CN105552348B
CN105552348B CN201510818762.7A CN201510818762A CN105552348B CN 105552348 B CN105552348 B CN 105552348B CN 201510818762 A CN201510818762 A CN 201510818762A CN 105552348 B CN105552348 B CN 105552348B
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Prior art keywords
lithium
aluminium sheet
aluminium
negative pole
sheet circle
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CN105552348A (en
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郝德利
叶丽光
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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
    • 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

The present invention, which provides a kind of 3V, can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole.Two diameter identical disks are swept away on the aluminium sheet of purity more than 99%, stamp out donut connected in star above a disk wherein（Such as figure）Oil removing and water removal drying are carried out to aluminium sheet circle, in dry environment of the relative humidity less than 1%, aluminium sheet circle/lithium piece/aluminium sheet circle is stacked together, outside applies pressure and kept for more than 10 seconds, make three's cold rolling together, obtain lithium-aluminium alloy negative pole, the interface of donut connected in star is circular arc, width 0.5mm, arc radius 0.3mm, the distance between annulus is 0.8mm, between 0.8 ~ 1.0, aluminium sheet circle/lithium block/aluminium sheet circle is stacked together for metal lithium sheet and the mol ratio of aluminium flake, and the concentric ring recesses on aluminium sheet circle face lithium metal block.The inventive method technique is simple, is adapted to the extensive quick production of industrialization, while has 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：
Two diameter identical disks are swept away on the aluminium sheet of purity more than 99%, are stamped out wherein above a disk Donut connected in star（Fig. 1）, oil removing and water removal drying are carried out to aluminium sheet circle, in dry environment of the relative humidity less than 1%, Aluminium sheet circle/lithium block/aluminium sheet circle is stacked together, and outside applies pressure and kept for more than 10 seconds, makes three's cold rolling together, obtains To lithium-aluminium alloy negative pole, the interface of described donut connected in star is circular arc, width 0.5mm, and arc radius is The distance between 0.3mm, annulus is 0.8mm；The mol ratio of described lithium metal block and two aluminium sheet circles is between 0.8 ~ 1.0； Described aluminium sheet circle/lithium block/aluminium sheet circle is stacked together, and the concentric ring recesses on aluminium sheet circle face lithium metal block.
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.Due to having concentric ring groove on one of aluminium sheet circle, in lithium piece and aluminium flake During cold rolling together, concentric circular direction flow behavior is often presented in lithium metal, and lithium metal can be full of groove, be clipped in two layers Between aluminium sheet circle, contact area is expanded, time and the distance of diffusion is shortened, improves the formation speed of lithium-aluminium alloy, can To be immediately available for battery assembling, the purpose of quick production is reached, 500 is improved than method unit production capacity disclosed in CN87100735 More than times.On the other hand, first in discharge process, in the presence of energy of position, lithium ion passes through the metallic aluminum on upper strata, enters Positive pole, formed than more uniform ion channel, so as to improve the cycle life of negative pole.Under 0.1C, 72% charging and discharging depth Circulation, when its capacity is less than the 72% of initial value, cycle-index has reached 100 times.
Brief description of the drawings
Fig. 1 is the structural representation of aluminium sheet circle
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 0.25mm aluminium sheet on, diameter 9mm disks 2 are swept away, wherein on an aluminium sheet circle Go out concentric annular groove 4, slot cross-section arc radius is 0.3mm, well width 0.5mm, and 4 grooves are equally spaced, then oil removing, clear After washing, in 105 DEG C of forced air dryings 2 hours；
（3）Relative humidity be 0.9% drying room in, the aluminium sheet circle for having annular groove is put into negative electrode casing, annular groove upward, Aluminium sheet circle is forced with 0.5MPa with plastics pressure head on pneumatic press, 3 seconds, aluminium sheet circle is fixed on inside negative electrode casing, Battery grade lithium metal piece 10mg cubic blocks are placed among aluminium sheet circle, then cover another aluminium sheet circle, are applied with drift in aluminium sheet circle 10MPa pressure, pressure is removed after being kept for 10 seconds, button lithium battery lithium-aluminium alloy negative pole can be filled by obtaining 3V.
（4）PP barrier films are put on negative pole, add 0.2g electrolyte 1M LiPF6/ (EC+DMC+PC), then on barrier film Pressure lithium manganate anode slice is lowerd, finally covers anode cover, seals, obtains ML1220 button cells.
（5）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）Purity 99%, thickness 0.25mm aluminium sheet on, diameter 9mm disks 2 are swept away, wherein on an aluminium sheet circle Go out concentric annular groove 4, slot cross-section arc radius is 0.3mm, well width 0.5mm, and 4 grooves are equally spaced, then oil removing, clear After washing, in 105 DEG C of forced air dryings 2 hours；
（3）Relative humidity be 0.9% drying room in, the aluminium sheet circle for having annular groove is put into negative electrode casing, annular groove upward, Aluminium sheet circle is forced with 0.5MPa with plastics pressure head on pneumatic press, 3 seconds, aluminium sheet circle is fixed on inside negative electrode casing, Battery grade lithium metal piece 8mg cubic blocks are placed among aluminium sheet circle, then cover another aluminium sheet circle, are applied with drift in aluminium sheet circle 10MPa pressure, pressure is removed after being kept for 10 seconds, button lithium battery lithium-aluminium alloy negative pole can be filled by obtaining 3V.
（4）PP barrier films are put on negative pole, 0.2g electrolyte 1M LiPF6/ (EC+DMC+PC) are added, then on barrier film Pressure lithium manganate anode slice is lowerd, finally covers anode cover, seals, obtains ML1220 button cells.
（5）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.

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：In the aluminium of purity more than 99% Two identical disks are swept away on plate, donut connected in star is stamped out above a disk wherein, aluminium sheet circle is removed Oil and water removal drying, it is in dry environment of the relative humidity less than 1%, aluminium sheet circle/lithium block/aluminium sheet circle is stacked together, it is outside Apply pressure to be kept for more than 10 seconds, make three's cold rolling together, obtain lithium-aluminium alloy negative pole.
2. a kind of 3V described in claim 1 can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole, it is characterised in that：Institute The interface for the donut connected in star stated is circular arc, width 0.5mm, arc radius 0.3mm, and the distance between annulus is 0.8mm。
3. a kind of 3V described in claim 1 can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole, it is characterised in that：Institute The mol ratio of the lithium block stated and two aluminium sheet circles is between 0.8 ~ 1.0.
CN201510818762.7A 2015-11-23 2015-11-23 A kind of 3V can fill the preparation method of button lithium battery lithium-aluminium alloy negative pole Active CN105552348B (en)

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CN109659490B (en) * 2019-01-07 2024-03-26 宁波必霸能源有限公司 Button cell lithium negative electrode forming equipment and forming method
CN109904417A (en) * 2019-01-29 2019-06-18 电子科技大学 A kind of lithium-dissimilar metal composite negative pole material and preparation method thereof
RU2020121620A (en) * 2020-06-25 2021-12-27 Григорий Аврамович Радуцкий Method of increasing the discharge capacity of a lithium-ion battery
CN112802997B (en) * 2021-02-24 2022-05-24 华南理工大学 Lithium metal battery with curved surface lithium piece negative pole

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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
CN101290987A (en) * 2008-06-05 2008-10-22 天津中能锂业有限公司 Minus pole of coin type lithium battery, preparing method thereof and coin type lithium battery comprising the minus pole
CN101752612A (en) * 2008-12-15 2010-06-23 山东神工海特电子科技有限公司 Method for producing 3V chargeable lithium manganese dioxide cell
CN102610848A (en) * 2011-01-21 2012-07-25 天津赫维科技有限公司 Chargeable 3V button-type lithium battery
CN103290293A (en) * 2013-06-05 2013-09-11 四川天齐锂业股份有限公司 Lithium-aluminum alloy, and production method and use thereof

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JP3304367B2 (en) * 1991-09-27 2002-07-22 エフ・ディ−・ケイ株式会社 Method for producing negative electrode alloy for lithium secondary battery
JP3701900B2 (en) * 2000-12-11 2005-10-05 日立マクセル株式会社 Method for producing non-aqueous electrolyte battery
JP5176386B2 (en) * 2006-09-12 2013-04-03 ソニー株式会社 Non-aqueous electrolyte battery

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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
CN101290987A (en) * 2008-06-05 2008-10-22 天津中能锂业有限公司 Minus pole of coin type lithium battery, preparing method thereof and coin type lithium battery comprising the minus pole
CN101752612A (en) * 2008-12-15 2010-06-23 山东神工海特电子科技有限公司 Method for producing 3V chargeable lithium manganese dioxide cell
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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