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CN1571198A - Lithium secondary battery anode and lithium secondary battery using the same - Google Patents

Lithium secondary battery anode and lithium secondary battery using the same Download PDF

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Publication number
CN1571198A
CN1571198A CNA03139826XA CN03139826A CN1571198A CN 1571198 A CN1571198 A CN 1571198A CN A03139826X A CNA03139826X A CN A03139826XA CN 03139826 A CN03139826 A CN 03139826A CN 1571198 A CN1571198 A CN 1571198A
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Prior art keywords
secondary battery
positive electrode
lithium secondary
lithium
absorbing agent
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Inventor
黄文正
黄全德
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Priority to CNA03139826XA priority Critical patent/CN1571198A/en
Publication of CN1571198A publication Critical patent/CN1571198A/en
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

本发明涉及一种锂二次电池正极，该正极包括正极活性材料及分散于正极活性材料中的吸水剂。正极活性材料包括锂锰氧化物、锂镍氧化物、锂钴氧化物等锂与过渡金属的复合氧化物；吸水剂包括锂化分子筛、活性炭、活性氧化铝、硅胶、氧化钙、硫酸钙等，具有露点低于－56℃的强吸水性。吸水剂能完全吸附锂二次电池制程中残留及使用时水分子气透性渗入的水份，防止锂离子电池中毒，从而提高锂二次电池使用寿命。本发明还涉及一种使用该正极的锂二次电池。

Figure 03139826

The invention relates to a positive pole of a lithium secondary battery, which comprises a positive pole active material and a water absorbing agent dispersed in the positive pole active material. Positive electrode active materials include composite oxides of lithium and transition metals such as lithium manganese oxide, lithium nickel oxide, and lithium cobalt oxide; water absorbents include lithiated molecular sieves, activated carbon, activated alumina, silica gel, calcium oxide, calcium sulfate, etc. It has strong water absorption with a dew point below -56°C. The water-absorbing agent can completely absorb the moisture remaining in the lithium secondary battery manufacturing process and the water molecules infiltrated by the gas permeability during use, so as to prevent the lithium ion battery from being poisoned, thereby improving the service life of the lithium secondary battery. The present invention also relates to a lithium secondary battery using the positive electrode.

Figure 03139826

Description

Cathode plate for lithium secondary battery and use this anodal lithium secondary battery
[technical field]
The present invention relates to lithium secondary battery, relate in particular to a kind of cathode plate for lithium secondary battery.
[background technology]
Lithium secondary battery has been widely used in the consumption electronic products such as mobile phone, notebook computer because it has good characteristics such as high-energy-density, high electromotive force and low self-discharge.
Lithium secondary battery of the present invention comprises lithium ion battery and high-polymer lithium battery.Lithium ion battery be with material with carbon elements such as Delanium or native graphites as negative pole, with metal oxides such as lithium cobalt, lithium nickel, lithium manganese as positive electrode, with the secondary cell of anhydrous organic solvent as electrolyte.High-polymer lithium battery comprises two classes, and a class is that electrode is the lithium ion battery of macromolecular material, and another kind of is that electrolyte is the lithium ion battery of solid-state or colloidal state polymer.
Lithium secondary battery all adopts organic solvent or organic polymer as electrolyte, require inside battery moisture-free, because lithium ion battery voltage is up to 3～4V, and the decomposition voltage of water is 1.23V, if inside battery contains moisture content, discharge and recharge moisture content decomposition down at high voltage, can cause degradation of cell performance, reduce the useful life of lithium secondary battery.
Therefore, need strict control relative air humidity less than 0.04% (being Dew point=-56 ℃) in the battery processing procedure.But the control relative air humidity needs expensive less than 0.04%, and still can't avoid residual a certain amount of hydrone in the preparation process.In addition, lithium secondary battery also can't be avoided the hydrone impervious after long-term the use, causes the battery functi on forfeiture.
[summary of the invention]
The purpose of this invention is to provide a kind of inside battery hydrone that prevents and make the positive pole of lithium secondary battery performance degradation.
Another purpose of the present invention provides a kind of lithium secondary battery that contains above-mentioned positive pole.
The invention provides a kind of cathode plate for lithium secondary battery, this positive pole comprises positive electrode active materials and is scattered in water absorbing agent in the positive electrode active materials, and positive electrode active materials comprises the composite oxides of lithium such as lithium manganese oxide, lithium nickel oxide, lithium and cobalt oxides and transition metal; Water absorbing agent comprises lithiumation molecular sieve, activated carbon, activated alumina, silica gel, calcium oxide, calcium sulfate etc., has dew point to be lower than-56 ℃ strong absorptive, and particle size range is 2 nanometers to 10 micron.
The present invention also provides a kind of lithium secondary battery that contains above-mentioned positive pole.
Compared with prior art, positive pole provided by the invention has the following advantages: water absorbing agent makes an addition in the positive electrode active materials, can adsorb the residual or moisture content that infiltrates when using in the lithium secondary battery processing procedure fully, reduce the cell preparation cost, prevent that lithium ion battery is poisoned in the battery use, thereby prolong the useful life of lithium secondary battery.
[description of drawings]
Fig. 1 is a cathode plate for lithium secondary battery structural representation of the present invention.
Fig. 2 is a lithium secondary battery internal structure schematic diagram of the present invention.
[embodiment]
As shown in Figure 1, cathode plate for lithium secondary battery 10 of the present invention comprises collector body 101, positive electrode active materials 102, is scattered in water absorbing agent 103 and binding agent (figure does not indicate) in the positive electrode active materials, positive electrode active materials 102 forms one with water absorbing agent 1 03 by binding agent, is coated on the surface of collector body 101.Wherein water absorbing agent 103 comprises lithiumation molecular sieve, activated carbon, activated alumina, silica gel, calcium oxide, calcium sulfate etc., has dew point to be lower than-56 ℃ strong absorptive, and particle size range is 2 nanometers to 10 micron; Positive electrode active materials 102 comprises the composite oxides of lithiums such as lithium manganese oxide, lithium nickel oxide, lithium and cobalt oxides and transition metal; Collector body 101 is metal base or carbon-point, has excellent conductive performance; Binding agent generally uses polytetrafluoroethylene, Kynoar, polyacrylonitrile, poly(ethylene oxide), ethylene-propylene rubber etc.
The preparation method of cathode plate for lithium secondary battery of the present invention may further comprise the steps:
Positive electrode active materials 102 powders, water absorbing agent 103 and binding agent are mixed, and the suitable dispersant (as the N-methyl pyrrolidone) of using the solubilized binding agent is coated on collector body 101 surfaces with after its dispersion, the pulp with slurries, dry getting final product.
As shown in Figure 2, lithium secondary battery 20 of the present invention comprises a housing (figure indicates) and places housing interior negative pole 11, electrolyte 12, barrier film 13 and provided by the present invention anodal 10.
The negative pole 11 of lithium ion battery and high-polymer lithium battery mainly comprises collector body and is formed at the active material on collector body surface, as material with carbon element, comprise graphite, carbon dust, carbon fiber or carbon nano-tube, in addition, some transition metal or its oxide also can be selected for use, as tin and oxide thereof.
Electrolyte 12 is the general organic electrolyte solution of lithium ion battery, can be added one or more solvable lithium salts by the mixed solvent that a kind of organic solvent or several organic solvent are formed and form.Organic solvent is propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1 for example, 2-dimethoxy-ethane etc., typical solvable lithium salts such as lithium perchlorate, LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium etc.
For high-polymer lithium battery, electrolyte 12 is polymer dielectric, as contains polyethylene oxygen alkane, polypropylene oxygen alkane, polyacrylonitrile, polyvinyl chloride, Kynoar of lithium salts such as lithium perchlorate, LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium etc.
Battery isolating film 13 as inorganic paper, adhesive-bonded fabric, high molecular polymer perforated membrane etc., comprises monofilm and multilayer film for the lithium secondary battery barrier film that prior art adopted.
Battery container comprises metal, alloy, plastics or its combination.
Lithium secondary battery of the present invention can have Any shape, as cylindric, prism-shaped, sheet or button-type.
The preparation of lithium secondary battery of the present invention can be adopted the known method for preparing lithium secondary battery of any public.Particularly, a kind of method commonly used is included in positive pole 10 and the negative pole of placing in the housing (figure indicate) by barrier film 13 couplings 11, subsequently toward wherein injecting electrolyte and with its sealing.The electrolytical method of preferred vacuum injection conduct injection, but it is not particularly limited.Also the electrode 10,11 of coupling can be flooded with electrolyte solution before in placing housing.
Compared with prior art, positive electrode provided by the invention has the following advantages: water absorbing agent makes an addition in the positive electrode active materials, can adsorb the residual or moisture content that infiltrates when using in the lithium secondary battery processing procedure fully, reduce the cell preparation cost, prevent that lithium ion battery is poisoned in the battery use, thereby prolong the useful life of lithium secondary battery.

Claims (9)

1.一种锂二次电池正极，其特征在于其包括正极活性材料及分散于正极活性材料中的吸水剂。1. A lithium secondary battery positive pole, characterized in that it comprises a positive pole active material and a water absorbing agent dispersed in the positive pole active material. 2.如权利要求1所述的锂二次电池正极，其特征在于吸水剂包括锂化分子筛、活性碳、活性氧化铝、硅胶、氧化钙或硫酸钙。2. The positive electrode of lithium secondary battery according to claim 1, characterized in that the water absorbing agent comprises lithiated molecular sieves, activated carbon, activated alumina, silica gel, calcium oxide or calcium sulfate. 3.如权利要求1所述的锂二次电池正极，其特征在于吸水剂具有露点低于-56℃的强吸水性。3. The positive electrode of lithium secondary battery according to claim 1, characterized in that the water-absorbing agent has a strong water-absorbing property with a dew point lower than -56°C. 4.如权利要求1所述的锂二次电池正极，其特征在于吸水剂的粒径范围为2纳米到10微米。4. The positive electrode of lithium secondary battery according to claim 1, characterized in that the particle size of the water-absorbing agent ranges from 2 nanometers to 10 microns. 5.如权利要求1所述的锂二次电池正极，其特征在于正极活性材料包括锂锰氧化物、锂镍氧化物或锂钴氧化物。5. The lithium secondary battery positive electrode according to claim 1, wherein the positive electrode active material comprises lithium manganese oxide, lithium nickel oxide or lithium cobalt oxide. 6.如权利要求1所述的锂二次电池正极，其特征在于该正极还包括集电体及粘结剂，正极活性材料与吸水剂通过粘结剂粘结形成一体，涂覆于集电体的表面。6. The positive electrode of lithium secondary battery as claimed in claim 1, characterized in that the positive electrode also includes a current collector and a binder, the positive electrode active material and the water absorbing agent are bonded to form one body through the binder, and coated on the current collector body surface. 7.如权利要求6所述的锂二次电池正极，其特征在于集电体包括金属基材或碳棒。7. The positive electrode of lithium secondary battery according to claim 6, characterized in that the current collector comprises a metal substrate or a carbon rod. 8.如权利要求6所述的锂二次电池正极，其特征在于粘结剂包括聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、聚环氧乙烷或乙丙橡胶。8. The lithium secondary battery positive electrode according to claim 6, wherein the binder comprises polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene oxide or ethylene propylene rubber. 9.一种锂二次电池，包括壳体以及置于壳体内的正极、负极、有机电解质及隔离膜，其特征在于该正极包括正极活性材料及分散于正极活性材料中的吸水剂。9. A lithium secondary battery comprising a casing and a positive electrode placed in the casing, a negative electrode, an organic electrolyte and a separator, characterized in that the positive electrode includes a positive electrode active material and a water absorbing agent dispersed in the positive electrode active material.
CNA03139826XA 2003-07-12 2003-07-12 Lithium secondary battery anode and lithium secondary battery using the same Pending CN1571198A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101710623B (en) * 2009-11-24 2011-06-15 武汉孚安特科技有限公司 Method for solving gas expansion of lithium-manganese dioxide flexible packaging battery and cathode material of lithium-manganese dioxide flexible packaging battery
CN102709521A (en) * 2012-06-12 2012-10-03 宁德新能源科技有限公司 Lithium ion battery and anode thereof
CN103268958A (en) * 2013-05-22 2013-08-28 江苏富朗特新能源有限公司 Processing method of lithium-ion battery electrolyte
CN105406040A (en) * 2015-11-03 2016-03-16 湖南长远锂科有限公司 Coated and modified high-nickel ternary cathode material and preparation method thereof
CN106848379A (en) * 2015-11-11 2017-06-13 株式会社Lg化学 Electrode for lithium secondary battery containing hygroscopic substance and lithium secondary battery containing same
CN107069018A (en) * 2015-12-03 2017-08-18 通用汽车环球科技运作有限责任公司 Addition dries metal oxide or metal nitride particles to improve battery cycle life and power-performance
CN109742391A (en) * 2019-01-10 2019-05-10 上海大学(浙江·嘉兴)新兴产业研究院 A kind of nickelic lithium ion battery, cell positive material and preparation method thereof
US10490821B2 (en) 2015-11-11 2019-11-26 Lg Chem, Ltd. Electrode for lithium secondary battery comprising hygroscopic material and lithium secondary battery comprising the same
CN112216814A (en) * 2020-12-09 2021-01-12 江苏时代新能源科技有限公司 Electrode pole piece, secondary battery and preparation method thereof, and device containing secondary battery

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101710623B (en) * 2009-11-24 2011-06-15 武汉孚安特科技有限公司 Method for solving gas expansion of lithium-manganese dioxide flexible packaging battery and cathode material of lithium-manganese dioxide flexible packaging battery
CN102709521A (en) * 2012-06-12 2012-10-03 宁德新能源科技有限公司 Lithium ion battery and anode thereof
CN103268958A (en) * 2013-05-22 2013-08-28 江苏富朗特新能源有限公司 Processing method of lithium-ion battery electrolyte
CN105406040B (en) * 2015-11-03 2019-01-11 湖南长远锂科有限公司 Nickelic tertiary cathode material of coating modification and preparation method thereof
CN105406040A (en) * 2015-11-03 2016-03-16 湖南长远锂科有限公司 Coated and modified high-nickel ternary cathode material and preparation method thereof
CN106848379A (en) * 2015-11-11 2017-06-13 株式会社Lg化学 Electrode for lithium secondary battery containing hygroscopic substance and lithium secondary battery containing same
CN106848379B (en) * 2015-11-11 2019-07-26 株式会社Lg化学 Hygroscopic substance-containing electrode for lithium secondary battery and lithium secondary battery including the same
US10490821B2 (en) 2015-11-11 2019-11-26 Lg Chem, Ltd. Electrode for lithium secondary battery comprising hygroscopic material and lithium secondary battery comprising the same
CN107069018A (en) * 2015-12-03 2017-08-18 通用汽车环球科技运作有限责任公司 Addition dries metal oxide or metal nitride particles to improve battery cycle life and power-performance
US10461373B2 (en) 2015-12-03 2019-10-29 GM Global Technology Operations LLC Adding dry metal oxide for metal nitride particles to improve battery cycle life and power performance
CN109742391A (en) * 2019-01-10 2019-05-10 上海大学(浙江·嘉兴)新兴产业研究院 A kind of nickelic lithium ion battery, cell positive material and preparation method thereof
CN109742391B (en) * 2019-01-10 2021-12-07 上海大学(浙江·嘉兴)新兴产业研究院 High-nickel lithium ion battery, battery positive electrode material and preparation method thereof
CN112216814A (en) * 2020-12-09 2021-01-12 江苏时代新能源科技有限公司 Electrode pole piece, secondary battery and preparation method thereof, and device containing secondary battery
WO2022121571A1 (en) * 2020-12-09 2022-06-16 江苏时代新能源科技有限公司 Electrode pole piece, secondary battery and preparation method therefor, and device comprising secondary battery
EP4148818A4 (en) * 2020-12-09 2024-02-28 Jiangsu Contemporary Amperex Technology Limited Electrode pole piece, secondary battery and preparation method therefor, and device comprising secondary battery

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