CN107093706A - Cathode of lithium battery preparation method - Google Patents

Cathode of lithium battery preparation method Download PDF

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Publication number
CN107093706A
CN107093706A CN201710338720.2A CN201710338720A CN107093706A CN 107093706 A CN107093706 A CN 107093706A CN 201710338720 A CN201710338720 A CN 201710338720A CN 107093706 A CN107093706 A CN 107093706A
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CN
China
Prior art keywords
cathode
lithium
layer
lithium battery
material layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710338720.2A
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Chinese (zh)
Inventor
宋殿权
张春涛
王永鹤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HARBIN COSLIGHT POWER CO Ltd
Original Assignee
HARBIN COSLIGHT POWER CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by HARBIN COSLIGHT POWER CO Ltd filed Critical HARBIN COSLIGHT POWER CO Ltd
Priority to CN201710338720.2A priority Critical patent/CN107093706A/en
Priority to PCT/CN2017/090252 priority patent/WO2018209762A1/en
Publication of CN107093706A publication Critical patent/CN107093706A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

Cathode of lithium battery preparation method, is related to solid state battery and liquid state batteries field.The present invention is low in order to solve graphite cathode gram specific capacity traditional at present, and dendrite easily grows, and coulombic efficiency is low first, the problem of battery energy density is low.Absorption or porous intermediate material layer are mixed to form according to a certain ratio Step 1: conductive agent and weight/mass percentage composition that the carbons material for being 75%~90% by weight/mass percentage composition, weight/mass percentage composition are 5%~20% are 5%~10% binding agent, then intermediate material layer is coated on a current collector according to 1um~70um thickness；Step 2: uniform on intermediate material layer steam the metallic lithium layer or metallic sodium layer for crossing that thickness is 1um~30um；Step 3: after the operation of completion step one and step 2, by lug connection on a current collector, completing the preparation of cathode of lithium battery.It is applied in solid state battery field and liquid state batteries field.

Description

Cathode of lithium battery preparation method
Technical field
The present invention relates to cathode of lithium battery preparation method.Belong to solid state battery and liquid state batteries field.
Background technology
Compared to the graphite cathode being applied in current business in lithium ion battery, lithium an- ode can be provided in theory More capacity (3860mAh/g, graphite cathode：370mAh/g), lithium an- ode is expected in portable electric appts of future generation And larger application is realized in the field such as electric automobile.It is that the lithium-sulfur cell of negative pole and the empty battery of lithium are gradually ground using lithium metal Study carefully the concern of people, the focus as academic and industrial circle research in recent years.But, also there is many and ask in the research of lithium an- ode Topic, most important of which one is the growth of dendrite.During dendrite is due to lithium-ion negative pole Multiple depositions/precipitation process, bear The dendritic lithium deposit that pole occurs.The problem of dendritic growth can bring two aspects：(1) dendrite, which can pierce through barrier film, causes electricity Short circuit current flow inside pond short circuit, both positive and negative polarity causes battery system thermal runaway, and then trigger batteries caught fire in inside battery heat Even blast etc. a series of safety problems；(2) dendrite can increase the side reaction of electrolyte and lithium metal, consume lithium active material, Reduce battery utilization rate.The Li dendrite for departing from collector is dead lithium, and the appearance of dead lithium can reduce available active material, drop The efficiency and cycle life of low battery.
The appearance of Li dendrite can not be fundamentally avoided at present, and the lithium battery based on lithium anode is still in laboratory rank Section, rarely has industry efforts appearance.
The content of the invention
The present invention is low in order to solve graphite cathode gram specific capacity traditional at present, and dendrite easily grows, first coulombic efficiency It is low, the problem of battery energy density is low.Cathode of lithium battery preparation method is now provided.
Cathode of lithium battery preparation method, this method comprises the following steps：
Step 1: the carbons material for being 75%~90% by weight/mass percentage composition, weight/mass percentage composition are 5%~20% Conductive agent and weight/mass percentage composition carry out being mixed to form absorption or porous intermediate material layer for 5%~10% binding agent, Intermediate material layer is coated on a current collector according to 1um~70um thickness again；
Step 2: uniform on intermediate material layer steam the metallic lithium layer or metallic sodium layer for crossing that thickness is 1um~30um；
Step 3: after the operation of completion step one and step 2, by lug connection on a current collector, completing cathode of lithium battery Preparation.
Beneficial effects of the present invention are：
The cathode of lithium battery of the present invention is by the collector of bottom, intermediate material layer and the metal being attached on intermediate material layer Lithium layer or metallic sodium layer are constituted, wherein, the component that intermediate material layer is represented by following weight/mass percentage composition is constituted：Carbons material 75%~90%, conductive agent 5%~20% and binding agent 5%~10%, the thickness of intermediate material layer is 1um~70um；Metal Lithium layer or metallic sodium layer cross lithium metal through steaming and obtained on intermediate material layer, wherein, metallic lithium layer or metallic sodium thickness degree are 1um Metallic lithium layer or the metallic sodium layer of~30um dense uniform.The cathode of lithium battery of the present invention, can be adjusted using intermediate material layer Control distribution of the lithium ion in negative terminal surface, it is to avoid the aggregation of lithium ion battery over time and space, realize lithium ion in negative pole Being uniformly distributed for surface, so as to suppress the appearance of Li dendrite, improves the security performance of lithium metal battery.The cathode of lithium battery with Coupled with height ratio capacity positive electrode such as sulphur, air etc., for constructing high-energy-density, high stability, high security Lithium battery system is significant.
The cathode of lithium battery that the application is constituted can be applied in solid state battery field and liquid state batteries field, steam the lithium gold crossed Category or metallic sodium can suppress the generation of lithium Zhi Jing in battery charge and discharge process, improve the security of battery, and this new Type cathode of lithium battery can reduce battery irreversible capacity loss in formation process, improve the coulombic efficiency first of battery, Afterwards play positive electrode gram volume and improve 3%-20%.
The cathode of lithium battery of the application and nickel cobalt aluminium tertiary cathode material are assembled into button cell, battery first imitate by coulomb Rate is 97%, and uses traditional graphite cathode and nickel cobalt aluminium tertiary cathode material to be assembled into button cell, its first coulomb imitate Rate is 92%.
The cathode of lithium battery of the application and nickel cobalt aluminium tertiary cathode material are assembled into button cell, circulation 200 weeks is carried out Capacity attenuation 1.8%, and use simple metal lithium piece to do negative pole and be assembled into button cell with nickel cobalt aluminium tertiary cathode material, circulate 200 weeks capacity attenuations 3.4%.
The cathode of lithium battery of the application is matched into identical nickel cobalt aluminium tertiary cathode material, this Shen compared with conventional graphite negative pole Cathode of lithium battery quality please than conventional graphite negative pole mitigate 10%~80%, thickness compared to traditional negative pole be thinned 10%~ 90%.
So, the negative pole quality for the cathode of lithium battery that the application is constituted mitigates 10%~80%, thickness than conventional graphite negative pole Degree is thinned 10%~90% compared to traditional negative pole, substantially increases gram specific capacity of negative material, can be by the energy of battery Density improves 1~4 times, improves the capacity usage ratio of battery.
Brief description of the drawings
Fig. 1 is the external structure schematic diagram of cathode of lithium battery, wherein, reference 1 represents intermediate material layer, reference 2 represent metallic lithium layer or metallic sodium layer, and reference 3 represents lug；
Fig. 2 is the internal structure schematic diagram of cathode of lithium battery, wherein, reference 4 represents collector (copper foil).
Embodiment
Embodiment one：Present embodiment, the lithium battery described in present embodiment are illustrated referring to Figures 1 and 2 Negative pole preparation method, this method comprises the following steps：
Step 1: the carbons material for being 75%~90% by weight/mass percentage composition, weight/mass percentage composition are 5%~20% Conductive agent and weight/mass percentage composition carry out being mixed to form absorption or porous intermediate material layer 1 for 5%~10% binding agent, Intermediate material layer 1 is coated on collector 4 according to 1um~70um thickness again；
Step 2: uniform on intermediate material layer 1 steam the metallic lithium layer or metallic sodium layer 2 for crossing that thickness is 1um~30um；
Step 3: after the operation of completion step one and step 2, lug 3 is connected on collector 4, completes lithium battery and bear The preparation of pole.
In present embodiment, distribution of the lithium ion in negative terminal surface can be regulated and controled using intermediate material layer, it is to avoid lithium ion The aggregation of battery over time and space, realizes lithium ion being uniformly distributed in negative terminal surface, so as to suppress the appearance of Li dendrite. The metallic lithium layer that the steaming is crossed to lithium ion by there is the intermediate material of stronger suction-operated layer to realize.The cathode of lithium battery Structure can effectively suppress the generation of Li dendrite, improve battery security, improve the capacity usage ratio of battery, such as coordinate high Specific capacity positive electrode is used, it will help promote the practicalization of novel high-energy metric density lithium battery.
In present embodiment, during weight/mass percentage composition represents that the quality of carbons material is accounted for for 75%~90% carbons material Between material layer 1 gross mass ratio be 75%~90%；Weight/mass percentage composition represents conductive agent for 5%~20% conductive agent The ratio that quality accounts for the gross mass of intermediate material layer 1 is 5%~20%；Weight/mass percentage composition represents for 5%~10% binding agent The ratio that the quality of binding agent accounts for the gross mass of intermediate material layer 1 is 5%~10%.
Embodiment two：Present embodiment is that the cathode of lithium battery preparation method described in embodiment one is made Further illustrate, in present embodiment, the intermediate material layer 1 that the carbons material coated on collector 4 is mixed to form refers to step Rapid one and the lithium metal or metallic sodium that cross is steamed on intermediate material layer 1, refer to step 2.
Embodiment three：Present embodiment is that the cathode of lithium battery preparation method described in embodiment one is made Further illustrate, in present embodiment, the carbons material in step one includes all kinds of soft carbon, hard carbon, silicon-carbon and graphite In one or more.
Embodiment four：Present embodiment is that the cathode of lithium battery preparation method described in embodiment one is made Further illustrate, in present embodiment, intermediate material layer 1, metallic lithium layer and metallic sodium layer are the active matter of cathode of lithium battery Matter.

Claims (4)

1. cathode of lithium battery preparation method, it is characterised in that this method comprises the following steps：
Step 1: the conduction that the carbons material for being 75%~90% by weight/mass percentage composition, weight/mass percentage composition are 5%~20% Agent and weight/mass percentage composition are that 5%~10% binding agent is mixed to form absorption or porous intermediate material layer according to a certain ratio (1), then by intermediate material layer (1) it is coated according to 1um~70um thickness on collector (4)；
Step 2: uniform on intermediate material layer (1) steam the metallic lithium layer or metallic sodium layer (2) for crossing that thickness is 1um~30um；
Step 3: after the operation of completion step one and step 2, lug (3) is connected on collector (4), completes lithium battery and bear The preparation of pole.
2. cathode of lithium battery preparation method according to claim 1, it is characterised in that the carbon coated on collector (4) The intermediate material layer (1) that class material is mixed to form, refers to step one and the lithium metal or metal crossed is steamed on intermediate material layer (1) Sodium, refers to step 2.
3. cathode of lithium battery preparation method according to claim 1, it is characterised in that the carbons material in step one includes One or more in soft carbon, hard carbon, all kinds of silicon-carbon and graphite.
4. cathode of lithium battery preparation method according to claim 1, it is characterised in that intermediate material layer (1), metallic lithium layer It is the active material of cathode of lithium battery with metallic sodium layer.
CN201710338720.2A 2017-05-15 2017-05-15 Cathode of lithium battery preparation method Pending CN107093706A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201710338720.2A CN107093706A (en) 2017-05-15 2017-05-15 Cathode of lithium battery preparation method
PCT/CN2017/090252 WO2018209762A1 (en) 2017-05-15 2017-06-27 Lithium battery anode and preparation method and application thereof

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Application Number Priority Date Filing Date Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110676433A (en) * 2018-07-03 2020-01-10 郑州宇通集团有限公司 Composite lithium cathode, preparation method thereof and lithium battery
CN114944477A (en) * 2022-05-25 2022-08-26 珠海鹏辉能源有限公司 Preparation method of metal lithium-carbon composite material and lithium battery

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CN112750978B (en) * 2020-12-30 2022-03-15 珠海冠宇电池股份有限公司 Pole piece and battery

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CN105977450A (en) * 2016-06-23 2016-09-28 盈天科技（深圳）有限公司 Method for plating lithium on anode plate of lithium ion battery
CN106558692A (en) * 2015-09-30 2017-04-05 中国科学院大连化学物理研究所 A kind of lithium battery negative pole and its preparation and application

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CN103066250A (en) * 2011-10-18 2013-04-24 上海德朗能动力电池有限公司 Lithium ion battery negative electrode with double-layer active substance structure and lithium ion battery with the same
CN102800865A (en) * 2012-08-28 2012-11-28 吴永胜 Lithium battery with total solid ions for conducting power
CN104409224A (en) * 2013-11-28 2015-03-11 东莞市长安东阳光铝业研发有限公司 Cathode plate for lithium-ion capacitor and production method of cathode plate
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Publication number Priority date Publication date Assignee Title
CN1378296A (en) * 2001-03-27 2002-11-06 日本电气株式会社 Anode for secondary battery and secondary battery with such anode
CN106558692A (en) * 2015-09-30 2017-04-05 中国科学院大连化学物理研究所 A kind of lithium battery negative pole and its preparation and application
CN105977450A (en) * 2016-06-23 2016-09-28 盈天科技（深圳）有限公司 Method for plating lithium on anode plate of lithium ion battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110676433A (en) * 2018-07-03 2020-01-10 郑州宇通集团有限公司 Composite lithium cathode, preparation method thereof and lithium battery
CN110676433B (en) * 2018-07-03 2021-07-27 郑州宇通集团有限公司 Composite lithium cathode, preparation method thereof and lithium battery
CN114944477A (en) * 2022-05-25 2022-08-26 珠海鹏辉能源有限公司 Preparation method of metal lithium-carbon composite material and lithium battery

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Application publication date: 20170825