CN102263232A - Lithium ion battery anode having composite metallic lithium structure - Google Patents

Lithium ion battery anode having composite metallic lithium structure Download PDF

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Publication number
CN102263232A
CN102263232A CN2011101494791A CN201110149479A CN102263232A CN 102263232 A CN102263232 A CN 102263232A CN 2011101494791 A CN2011101494791 A CN 2011101494791A CN 201110149479 A CN201110149479 A CN 201110149479A CN 102263232 A CN102263232 A CN 102263232A
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CN
China
Prior art keywords
lithium
barrier layer
lithium metal
ion battery
negative pole
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Pending
Application number
CN2011101494791A
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Chinese (zh)
Inventor
贾殷秋
杨毅
贾志杰
杨新建
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WUHAN HONGYANG TECHNOLOGY DEVELOPMENT Co Ltd
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WUHAN HONGYANG TECHNOLOGY DEVELOPMENT Co Ltd
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Application filed by WUHAN HONGYANG TECHNOLOGY DEVELOPMENT Co Ltd filed Critical WUHAN HONGYANG TECHNOLOGY DEVELOPMENT Co Ltd
Priority to CN2011101494791A priority Critical patent/CN102263232A/en
Publication of CN102263232A publication Critical patent/CN102263232A/en
Priority to PCT/CN2012/076046 priority patent/WO2012163247A1/en
Pending legal-status Critical Current

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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
    • H01M10/05—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
    • H01M4/134—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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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 invention relates to a lithium ion battery anode having a composite metallic lithium structure. The lithium ion battery anode is characterized in that: metallic lithium is taken as a core lithium ion battery anode material; a blocking layer is coated on the outer surface, opposite to an ionic membrane, of the metallic lithium, and has the functions of blocking the growth of lithium dendritic crystals towards the direction of the blocking layer and preventing the ionic membrane from being pierced; and holes capable of conducting electrolyte are formed in the blocking layer. The lithium ion battery anode having the composite metallic lithium structure can prevent the ionic membrane from being pierced by the lithium dendritic crystals and fully utilize the advantageous electrochemical properties of the metallic lithium.

Description

The lithium metal negative pole of lithium ion battery with compound structure
Technical field
The present invention relates to lithium ion battery, relate in particular to a kind of lithium metal negative pole of lithium ion battery with compound structure.
Background technology
The ion cathode material lithium of production usefulness is generally graphite nodule at present.Though researched and developed a lot of non-graphite cathode materials, operation principle is identical, promptly insert lithium/take off lithium, materials such as representative is tinbase, silica-based, aluminium lithium alloy.In these negative materials, the lithium ion efficiency of transmission of graphite is the highest, but capacity is low; Other material capacity height, but the lithium ion efficiency of transmission is lower.Yet, even graphite nodule, because its slotting lithium/take off the working method of lithium, transmission still has obstruction to lithium ion, and promptly high-rate performance is still limited.Lithium metal has high capacity (specific discharge capacity is more than 10 times of graphite theoretical value) and high lithium ion efficiency of transmission, and (lithium ion is directly long in the lithium grain outside, transmit no any resistance), do not have advantage such as decline, but repeatedly after the circulation, can form long dendrite, can pierce through ionic membrane (polyvinyl chloride folder polyethylene), make internal short-circuit of battery, cause potential safety hazard.Do negative pole though there is the human graphite nodule to mix with the lithium metal particle, with Li033VO266 and do not have that positive electrodes such as lithium oxide, sulfide match and.But in this case, lithium metal still may have grown into than the long shoot crystalline substance and pierces through ionic membrane.And owing to lithium metal not only chemical property is extremely active, oxidation very easily takes place in the efflorescence processing procedure, lithium metal was lost efficacy.
Summary of the invention
The objective of the invention is in order to solve the deficiency that the above-mentioned background technology exists, propose a kind ofly can prevent that ionic membrane from being pierced through by Li dendrite, bring into play the lithium metal negative pole of lithium ion battery with compound structure of metal lithium using electrochemical advantage performance more fully.
For achieving the above object, the present invention adopts following technical scheme: the lithium metal negative pole of lithium ion battery with compound structure, it is characterized in that adopting lithium metal as the lithium ion battery negative core material, be coated with in lithium metal and ionic membrane opposed outer surface and intercept Li dendrite and grow up, prevent to pierce through the barrier layer of ionic membrane effect towards the barrier layer direction, in barrier layer, be provided with can conducting electrolyte hole.This barrier layer can stop Li dendrite to be grown up towards the barrier layer direction, thereby the ionic membrane at the protection barrier layer back side is avoided being pierced through by Li dendrite.The bootable electrolyte stream of hole in the barrier layer guarantees that to lithium metal electrochemical process is unaffected.
Preferably, described barrier layer is a thin slice with holes.
Furtherly, the hole diameter of described thin slice with holes is the 10-100 micron.
Preferably, fill powder body material in the hole of described thin slice with holes, the micropore or the slit of perforation arranged between the powder body material particle, form crooked hole, both conducting electrolyte prevented again that Li dendrite from passing barrier layer, pierced through ionic membrane then.
Furtherly, described powder body material particle grain size is less than 1/3rd of barrier layer hole diameter.
Preferably, described barrier layer is a thin slice with holes, and its length and width size is greater than lithium metal length and width size, and the lithium metal two sides is clipped in the middle by barrier layer, and the edge of two sides barrier layer links to each other, and with lithium metal, forms a whole negative pole structure.
Preferably, the thickness of described barrier layer is the 5-100 micron.
Preferably, described barrier layer is a thin slice, and the length and width size on surface encases lithium metal greater than lithium metal surface length and width size with two barrier layers, two barrier layer edges link to each other, the hole of described barrier layer be after lithium metal and barrier layer combination on perforating press punching process.
Preferably, the thickness of described barrier layer is the 10-100 micron.
Preferably, utilize thickness greater than 20 microns, order number greater than 400 purpose nets, as barrier layer, two barrier layers are clamped metal lithium sheet, constitute negative pole.
The present invention has following characteristics:
1) lithium metal is the lithium ion battery negative core material.
2) for overcoming the defective (dendrite pierce through ionic membrane, cause short circuit) of lithium metal as lithium ion battery negative; employing coats outside lithium metal and intercepts the barrier layer that Li dendrite is grown up, and barrier layer has the function that stops Li dendrite to grow up, protect the ionic membrane at its back side not to be pierced towards the barrier layer direction.
3) be provided with in the barrier layer structure and can the lithium metal surface soaked into by electrolyte by electrolyte permeability, the hole that passes.
4) can bring into play electrochemistry advantage performances such as the big electric current of lithium metal, big capacity, high reversible, long circulation life more fully.
5) negative pole of the present invention can use by single face, also can two-sidedly use.Single face uses and is one deck positive pole, one deck negative pole; The two-sided use is one deck negative pole, and two-layer positive pole can improve the capacity density of lithium ion battery to greatest extent.
Description of drawings
Fig. 1 is embodiment 1 a described negative pole stereogram;
Fig. 2 is the cross-sectional view of Fig. 1;
Fig. 3 is a hole partial enlarged drawing in the barrier layer;
Fig. 4 is the cross-sectional view of Fig. 3;
Fig. 5 is embodiment 2 profiles;
Fig. 6 is that the present invention and two-layer positive pole are used state diagram.
Embodiment
Below in conjunction with the accompanying drawing illustrated embodiment the present invention is described in detail, so that those skilled in the art's understanding.
Embodiment 1: referring to Fig. 1 to Fig. 4.Present embodiment relates to a kind of lithium metal negative pole of lithium ion battery with compound structure, adopts sheet metal lithium 1 as the lithium ion battery negative core material.Between lithium metal 1 and ionic membrane 5 barrier layer 2 is set, barrier layer coated metal lithium is to stop Li dendrite along growing up perpendicular to the barrier layer direction.Described barrier layer 2 adopts 20～600 purpose copper mesh, also can adopt other hard material nets, preferred 200-500 order.This net adds small amount of binder and solvent with carbon black or other powder body material, is modulated into pasty state, is coated with extension one deck on the net at hard material, infiltrates mesh (will guarantee that each hole all is filled).The particle diameter of described powder body material particle 3 so just can make powder body material be filled in the mesh less than 1/3rd of mesh diameter.
After the above-mentioned net of making dried in the air, dries, sampling detects: net lay against on the glassware, drips electrolyte on the net, placed 1-5 hour, and whether observation electrolyte is penetrated into the another side of net.If infiltration is then qualified.At last, in hothouse, with two-layer this network folder layer of metal lithium sheet material (thickness will guarantee the need of two-layer positive electrode capacity, also wants many 50%), the two layers of mesh edge connects (welding) together.The length and width size of net is beneficial to protection greater than lithium metal sheet material length and width size.
Embodiment 2: referring to Fig. 5.Present embodiment lithium metal 1 is a flaky material, and barrier layer 2 is a copper sheet, and copper sheet thickness is greater than 10 microns, and its length and width size is greater than lithium metal sheet material length and width size.Live the lithium metal sheet material with two copper-clads, its edge links together, punching 4 on perforating press together then, negative pole.
Also can be behind one side sputter one deck lithium of copper sheet, punching 4 on perforating press together, the aperture is smaller as far as possible.
Embodiment 3: present embodiment lithium metal 1 is a flaky material, and barrier layer 2 is greater than 400 purpose nets, and thickness directly with two layers of mesh bag layer of metal lithium sheet, also can become negative pole greater than 20 microns.Figure slightly.
The negative pole of making according to the foregoing description, can cooperate with two-layer anodal 6 during use, referring to Fig. 6, can utilize negative pole core---the high power capacity of metal lithium sheet fully, and when improving the entire cell capacity, also improved the high-rate performance (depend on positive pole fully, negative pole is influence not) of battery.If anodal lithium can not fill or fill seldom (as oxide or sulfide), then barrier layer and metal lithium sheet can be adjacent to; If positive pole fills lithium (as LiMn2O4 or LiFePO 4), then metal lithium sheet will approach, and stays certain interval between barrier layer and metal lithium sheet.
Intercept the Li dendrite effect: embodiment 1 scheme the best, embodiment 2 schemes are taken second place, embodiment 3 schemes take second place again (because dendrite has filled up mesh, having formed bonding).
Under identical anodal 6 conditions, capacity improves effect: the battery capacity of embodiment scheme and embodiment 2 schemes improves above 50%; Embodiment 3 scheme battery capacities improve about 40%.Three embodiment scheme high-rate performances are all very good.
In sum, the present invention can prevent that ionic membrane 5 from being pierced through by Li dendrite, brings into play metal lithium using electrochemical advantage performance more fully.
Although the foregoing description has been made detailed description to the present invention; but those of ordinary skills can also make the not modification of off-center thought to it; as adopt the lithium metal of other shapes such as bulk or strip; these modifications all belong to protection scope of the present invention, and protection scope of the present invention should be as the criterion with claims.

Claims (10)

1. lithium metal negative pole of lithium ion battery with compound structure, it is characterized in that adopting lithium metal as the lithium ion battery negative core material, be coated with in lithium metal and ionic membrane opposed outer surface and intercept Li dendrite and grow up, prevent to pierce through the barrier layer of ionic membrane effect towards the barrier layer direction, in barrier layer, be provided with can conducting electrolyte hole.
2. lithium metal negative pole of lithium ion battery with compound structure according to claim 1 is characterized in that, described barrier layer is a thin slice with holes.
3. lithium metal negative pole of lithium ion battery with compound structure according to claim 2 is characterized in that, the hole diameter of described thin slice with holes is the 10-100 micron.
4. lithium metal negative pole of lithium ion battery with compound structure according to claim 2 is characterized in that, fills powder body material in the hole of described thin slice with holes, and the micropore or the slit of perforation arranged between the powder body material particle.
5. lithium metal negative pole of lithium ion battery with compound structure according to claim 4 is characterized in that, described powder body material particle grain size less than three of barrier layer hole diameter/
6. according at least one described lithium metal negative pole of lithium ion battery with compound structure of claim in the claim 1 to 5, it is characterized in that, described barrier layer is a thin slice with holes, its length and width size is greater than lithium metal length and width size, the lithium metal two sides is clipped in the middle by barrier layer, the edge of two sides barrier layer links to each other, and with lithium metal, forms a whole negative pole structure.
7. lithium metal negative pole of lithium ion battery with compound structure according to claim 6 is characterized in that, the thickness of described barrier layer is the 5-100 micron.
8. lithium metal negative pole of lithium ion battery with compound structure according to claim 1, it is characterized in that, described barrier layer is a thin slice, the length and width size on surface is greater than lithium metal surface length and width size, encase lithium metal with two barrier layers, two barrier layer edges link to each other, the hole of described barrier layer be after lithium metal and barrier layer combination on perforating press punching process.
9. lithium metal negative pole of lithium ion battery with compound structure according to claim 8 is characterized in that, the thickness of described barrier layer is the 10-100 micron.
10. lithium metal negative pole of lithium ion battery with compound structure according to claim 1 is characterized in that, utilize thickness greater than 20 microns, order number greater than 400 purpose nets, as barrier layer, two barrier layers are clamped metal lithium sheet, constitute negative pole.
CN2011101494791A 2011-06-03 2011-06-03 Lithium ion battery anode having composite metallic lithium structure Pending CN102263232A (en)

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CN2011101494791A CN102263232A (en) 2011-06-03 2011-06-03 Lithium ion battery anode having composite metallic lithium structure
PCT/CN2012/076046 WO2012163247A1 (en) 2011-06-03 2012-05-25 Lithium ion battery negative electrode with metallic lithium composite structure

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012163247A1 (en) * 2011-06-03 2012-12-06 武汉市弘阳科技发展有限公司 Lithium ion battery negative electrode with metallic lithium composite structure
CN103794755A (en) * 2014-02-21 2014-05-14 武汉市弘阳科技发展有限公司 Lithium ion battery negative electrode with lithium metal composite structure
CN103887074A (en) * 2014-03-19 2014-06-25 上海奥威科技开发有限公司 Lithium-ion capacitor long in service life
CN105470551A (en) * 2015-12-22 2016-04-06 中天储能科技有限公司 High-specific-energy and low-cost lithium ion battery
CN106876662A (en) * 2017-01-23 2017-06-20 浙江大学 A kind of metal electrode with three-dimensional structure
CN107665978A (en) * 2016-07-27 2018-02-06 现代自动车株式会社 Electrode of lithium secondary cell, the manufacture method of electrode and the lithium secondary battery including the electrode
CN108735970A (en) * 2018-04-20 2018-11-02 南京邮电大学 A kind of secondary cell sandwich structure metal composite negative pole piece
CN109616612A (en) * 2018-12-05 2019-04-12 珠海格力电器股份有限公司 A kind of electrode and lithium ion battery
CN111613772A (en) * 2020-04-21 2020-09-01 浙江锋锂新能源科技有限公司 Three-dimensional structure composite metal lithium cathode and preparation method thereof
CN112164804A (en) * 2020-09-29 2021-01-01 贵州梅岭电源有限公司 Preparation method of composite modified lithium metal soft package battery

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CN102263232A (en) * 2011-06-03 2011-11-30 武汉市弘阳科技发展有限公司 Lithium ion battery anode having composite metallic lithium structure

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CN202121011U (en) * 2011-06-03 2012-01-18 武汉市弘阳科技发展有限公司 Lithium ion battery cathode with metallic lithium composite structure

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012163247A1 (en) * 2011-06-03 2012-12-06 武汉市弘阳科技发展有限公司 Lithium ion battery negative electrode with metallic lithium composite structure
CN103794755A (en) * 2014-02-21 2014-05-14 武汉市弘阳科技发展有限公司 Lithium ion battery negative electrode with lithium metal composite structure
CN103887074A (en) * 2014-03-19 2014-06-25 上海奥威科技开发有限公司 Lithium-ion capacitor long in service life
CN105470551A (en) * 2015-12-22 2016-04-06 中天储能科技有限公司 High-specific-energy and low-cost lithium ion battery
CN107665978A (en) * 2016-07-27 2018-02-06 现代自动车株式会社 Electrode of lithium secondary cell, the manufacture method of electrode and the lithium secondary battery including the electrode
CN106876662A (en) * 2017-01-23 2017-06-20 浙江大学 A kind of metal electrode with three-dimensional structure
CN108735970A (en) * 2018-04-20 2018-11-02 南京邮电大学 A kind of secondary cell sandwich structure metal composite negative pole piece
CN108735970B (en) * 2018-04-20 2022-08-16 南京邮电大学 Sandwich structure metal composite negative plate for secondary battery
CN109616612A (en) * 2018-12-05 2019-04-12 珠海格力电器股份有限公司 A kind of electrode and lithium ion battery
CN109616612B (en) * 2018-12-05 2020-09-01 珠海格力电器股份有限公司 Electrode and lithium ion battery
CN111613772A (en) * 2020-04-21 2020-09-01 浙江锋锂新能源科技有限公司 Three-dimensional structure composite metal lithium cathode and preparation method thereof
CN111613772B (en) * 2020-04-21 2022-08-05 浙江锋锂新能源科技有限公司 Three-dimensional structure composite metal lithium cathode and preparation method thereof
CN112164804A (en) * 2020-09-29 2021-01-01 贵州梅岭电源有限公司 Preparation method of composite modified lithium metal soft package battery

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Application publication date: 20111130