CN101295802A - Safety lithium ion cell - Google Patents

Safety lithium ion cell Download PDF

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Publication number
CN101295802A
CN101295802A CNA2007100276882A CN200710027688A CN101295802A CN 101295802 A CN101295802 A CN 101295802A CN A2007100276882 A CNA2007100276882 A CN A2007100276882A CN 200710027688 A CN200710027688 A CN 200710027688A CN 101295802 A CN101295802 A CN 101295802A
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CN
China
Prior art keywords
diaphragm
lithium ion
anode
ion cell
active material
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Pending
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CNA2007100276882A
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Chinese (zh)
Inventor
赵丰刚
曾文辉
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Dongguan Amperex Electronics Technology Ltd
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Dongguan Amperex Electronics Technology Ltd
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Publication date
Application filed by Dongguan Amperex Electronics Technology Ltd filed Critical Dongguan Amperex Electronics Technology Ltd
Priority to CNA2007100276882A priority Critical patent/CN101295802A/en
Priority to PCT/CN2008/000096 priority patent/WO2008131631A1/en
Publication of CN101295802A publication Critical patent/CN101295802A/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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a safe Li-ion cell, anode diaphragm of which has relatively large resistance, which comprises an electrode array provided with an anode plate and a cathode plate, wherein, the anode plate comprises a current collector and a diaphragm which is adhered to the surface of the current collector and provided with an active substance, the active substance of the anode diaphragm adopts a graphite material and the resistance of the diaphragm of the anode plate is between 0.5 Omega cm<2> and 10 Omega cm<2>. As the resistance of the anode plate is relatively high and the contact resistance during short circuit is relatively low, the current density during short circuit is relatively low, thus causing no fire resulted from the sudden rise of temperature during the short circuit of the Li-ion cell and improving the safety of the Li-ion cell.

Description

Safety lithium ion cell
Technical field
The present invention relates to technical field of lithium ion, particularly a kind of anode diaphragm has the safety lithium ion cell of big resistance.
Background technology
Lithium ion battery is a kind of battery with high energy density and favorable environment protection energy, and it is widely used in all kinds of portable electric appts.Usually lithium ion battery comprises cathode sheets, barrier film and the anode strip of mutual coiling, and wherein cathode sheets comprises cathode current collector and diaphragm attached thereto, that have cathode active material; Anode strip comprises anode collector and diaphragm attached thereto, that have anode active material.Wherein cathode current collector generally adopts aluminium foil to make, and anode collector generally adopts Copper Foil to make, and isolation diaphragm generally adopts polypropylene and polyethylene laminated film.During making, cathode sheets, barrier film and anode strip stack back reeled makes battery, and battery is packed in the battery packages shell, then, injects electrolyte in pack case, makes battery after the sealing.
Yet, existing lithium ion battery is because the organic electrolyte of its use is inflammable, and its anode diaphragm generally uses graphite material, and its resistance is less relatively and also be easy to burning, when inside battery is short-circuited, is easy to cause battery burning and causes potential safety hazard.
Table one is the safety test result of one group of existing lithium ion battery, and its method of testing is: respectively anode collector, anode diaphragm in cathode current collector, negative electrode diaphragm and the anode strip are directly contacted, respectively test result is noted then.
Table one
Figure A20071002768800041
According to the result of above-mentioned test, when between cathode current collector in the cathode sheets (aluminium foil) and the anode diaphragm during short circuit, the temperature of battery can raise fast, begins to smolder, and produces naked light.Why produce this phenomenon and be because: the resistance of anode diaphragm is generally at 0.1～0.2 Ω/cm in the common lithium ion battery 2Between, and the cathodic coating sheet resistor is at 1.6 Ω/cm 2About, and anode material itself also be easy to the burning, like this, when cathode current collector directly contacts with the anode diaphragm, because resistance is less, its current density is relatively large, causes a large amount of heats to produce, and a large amount of heat that this moment, electric current produced concentrates on short circuit place, add anode material itself and also be easy to the characteristics of burning, cause burning just very easily, cause battery can't pass through above-mentioned short-circuit test, cause a hidden trouble to the safe handling of battery.
Summary of the invention:
Goal of the invention of the present invention is: a kind of safety lithium ion cell is provided, and particularly a kind of safety lithium ion cell of the anode diaphragm with big resistance is to overcome the problems referred to above.
To achieve the above object of the invention, the invention provides a kind of safety lithium ion cell, the anode strip of this lithium ion battery has higher resistance, and its resistance is generally at 0.5 Ω/cm 2～8 Ω/cm 2Like this, if run into fortuitous event, when piercing through barrier film and cause cathode current collector-aluminium foil to contact causing internal short-circuit with the anode diaphragm as the metallic particles that exists because of inside battery, because anode strip resistance is higher, contact resistance is less relatively during short circuit, short-circuit current density is also less relatively, so just can not cause lithium ion battery occur temperature raise suddenly cause on fire, thereby reach the fail safe that improves lithium ion battery.
For solving the problems of the technologies described above, the present invention has adopted following concrete scheme:
1, in the anode strip of battery, mix one or more insulating material, as titanium oxide (TiO 2), silica (SiO 2), aluminium oxide (Al 2O 3) or zinc oxide (ZnO 2) wait insulating material.
2, in the anode diaphragm, do not add conductive carbon powder, and increase the consumption of binding agent simultaneously.
3, adopt the graphite material of low conductivity, and graphite material is carried out surface treatment to reduce its conductance with metal oxide such as aluminium oxide (Al2O3) or magnesium oxide (MgO2).
Above-mentioned measure can be used separately, also can several schemes be used in combination.After adopting such scheme, the anode strip of lithium ion battery has higher resistance, and its resistance is generally at 0.5 Ω/cm 2～8 Ω/cm 2, preferred 1.4 Ω/cm 2, like this, can guarantee that battery is not on fire when short circuit, can make the capacity of battery again, cycle performances etc. are unaffected substantially.
Description of drawings:
The present invention is further illustrated below in conjunction with accompanying drawing:
Fig. 1 is the structural representation of lithium ion battery anode strip among the present invention.
Embodiment:
Execution mode one:
Safety lithium ion cell of the present invention, the technology that its structure and manufacture craft and present common lithium ion battery are made is basic identical, different is to adopt following method when making anode strip: see Fig. 1, anode strip 1 comprises anode collector 11 and diaphragm 12 attached thereto, that have anode active material in this experiment.The anode collector 11 general Copper Foils that adopt are made.During making at first, will be as the powdered graphite of negative active core-shell material, AL 2O 3Mix mutually with hydroxyl-methyl-sodium cellulosate (CMC) and butadiene-styrene rubber (SBR), wherein sodium cellulose glycolate and butadiene-styrene rubber are as binding agent.With this mixture be scattered in as in the water of solvent to obtain the anode mixture slurry.Then, above-mentioned slurry evenly coated on the negative current collector that Copper Foil makes make anode strip 1, cold pressing then.Then antianode sheet 1 carries out drying, allows solvent evaporates, and the anode strip surface forms one deck diaphragm 12 like this, and the temperature of drying can be selected as required.In addition, except that the mode that adopts coating, also can adopt the mode of dipping, with the surface of slurry attached to collector 11, cold pressing again, back to be dried forms one deck diaphragm 12 on collector 11 surfaces.
In order to improve experimental reliability, three groups of experiments have been done in the present embodiment altogether.
Experiment one
In this experiment, the mass percent of active material, binding agent and megohmite insulant is in the diaphragm 12: 94.5: 4: 1.5, wherein active material was: graphite, megohmite insulant adopts AL 2O 3, binding agent is: the mixture of CMC and SBR, the two mass percent in diaphragm is respectively: 1.5% and 2.5%.
Experiment two
Experiment two is identical with experiment one manufacture method, and that different is active material, binding agent and AL 2O 3The mass percent example.Three's mass percent is in this experiment: 91.5: 4: 4.5.Wherein, CMC and the SBR mass percent in diaphragm still is respectively: 1.5% and 2.5%.
Experiment three
Active material, binding agent and AL in this experiment 2O 3The mass percent example.Three's mass percent is in this experiment: 86.5: 4: 9.5.Wherein, CMC and the SBR mass percent in diaphragm still is divided into: 1.5% and 2.5%.
Comparative Examples
The same experiment manufacture method that adopts of contrast row, different is not contain AL in its diaphragm 2O 3, the mass percent of its active material and binding agent is: 96: 4.Wherein, CMC and the SBR mass percent in diaphragm still is respectively: 1.5% and 2.5%.
Table two is the data of above-mentioned three groups of experiments and the experimental result of resistance.
Table two
Figure A20071002768800071
Find out by data in the table, present relatively lithium ion battery, the resistive layer of anode strip surface membrane of the present invention obviously improves.After changing into, under the state that completely fills, all can be smoothly by the drift bolt test, particularly after battery was taken apart, it was on fire not smolder when directly anode strip being contacted with cathode current collector.And three groups of lithium ion batteries are adding AL 2O 3Other chemical property of back, as capacity, the cycle performance no significant difference promptly mixes AL in diaphragm 12 2O 3Can the performance of lithium ion battery not exerted an influence.
Execution mode two:
Execution mode two has also been done three groups of experiments and a Comparative Examples, and the experiment condition of three groups of experiments and the experiment condition of execution mode one are basic identical, just with Al 2O 3Use TiO 2Replace, Comparative Examples remains unchanged.Its experimental data and experimental result such as table three.
Table three
Figure A20071002768800081
Find out that by data in the table three three groups of lithium ion batteries are adding TiO in the present embodiment 2After also can significantly improve the anode film sheet resistor, thereby improve the lithium ion battery security energy, and other chemical property, as capacity, cycle performance does not have obviously poor.
Execution mode three
In the present embodiment, do not add megohmite insulant in the anode diaphragm, and adopt the lower graphite of conductivity, and suitably increase the content of binding agent as anode material.The percentage of graphite and binding agent exists: 90～92.5: between 10～7.5, and the resistance of the anode diaphragm of the above-mentioned substance of assurance employing simultaneously is at 0.5 Ω/cm 2～8 Ω/cm 2Between.After tested, the anode diaphragm that adopts above-mentioned material is at the battery of making, and it is on fire can not smolder when short-circuit test equally, satisfies the battery security requirement.
It is to be noted: thus invention thought of the present invention is for arriving the purpose that improves battery security by improving the anode bodies phase resistance; therefore should think: pass through variety of way; particularly disclosed several modes; no matter be to use separately or be used in combination, all should fall into protection scope of the present invention with the execution mode that improves the anode film sheet resistor.

Claims (6)

1, a kind of safety lithium ion cell, this lithium ion battery comprises an electrode group, the electrode group is provided with anode strip and cathode sheets, wherein anode strip comprises collector and is attached to the diaphragm that collection liquid surface has active material, the active material of anode diaphragm adopts graphite material, and it is characterized in that: resistance is at 0.5 Ω/cm in the diaphragm of this anode strip 2～10 Ω/cm 2Between.
2, safety lithium ion cell according to claim 1, it is characterized in that: the diaphragm on this anode strip surface comprises: active material, binding agent and as the aluminium oxide of megohmite insulant, its three's mass percent is: 86.5～94.5: 4: 9.5～1.5.
3, safety lithium ion cell according to claim 1, it is characterized in that: the diaphragm on this anode strip surface comprises: active material, binding agent and as the titanium oxide or the silica of megohmite insulant, its three's mass percent exists: 86.5～94.5: between 4: 9.5～1.5.
4, safety lithium ion cell according to claim 1 is characterized in that: the graphite material surface as anode diaphragm active material is coated with one deck aluminium oxide or magnesium oxide.
5, safety lithium ion cell according to claim 4 is characterized in that: exist through coating graphite material and the two mass percent of binding agent of handling: 93～94.5: between 7～5.5.
6, safety lithium ion cell according to claim 4 is characterized in that: it is characterized in that: described binding agent is: the mixture of sodium cellulose glycolate and butadiene-styrene rubber.
CNA2007100276882A 2007-04-25 2007-04-25 Safety lithium ion cell Pending CN101295802A (en)

Priority Applications (2)

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CNA2007100276882A CN101295802A (en) 2007-04-25 2007-04-25 Safety lithium ion cell
PCT/CN2008/000096 WO2008131631A1 (en) 2007-04-25 2008-01-14 Safety type battery

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101894937A (en) * 2010-07-02 2010-11-24 东莞新能源科技有限公司 Lithium ion battery and positive plate thereof
CN102934262A (en) * 2010-05-31 2013-02-13 日产自动车株式会社 Negative electrode for secondary battery, and process for production thereof
CN103531744A (en) * 2012-07-05 2014-01-22 苏州宝时得电动工具有限公司 Battery plate and electrode manufacturing method
CN112909228A (en) * 2021-01-13 2021-06-04 中科(马鞍山)新材料科创园有限公司 Modified negative pole piece and preparation method and application thereof
CN117039194A (en) * 2023-08-29 2023-11-10 中创新航科技集团股份有限公司 Cylindrical battery

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JP6729481B2 (en) * 2017-04-28 2020-07-22 トヨタ自動車株式会社 Laminated battery
PL3968430T3 (en) * 2020-03-27 2024-02-19 Contemporary Amperex Technology Co., Limited Secondary battery and apparatus containing the secondary battery

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
JPH10255807A (en) * 1997-03-13 1998-09-25 Matsushita Electric Ind Co Ltd Lithium ion secondary battery
KR100378014B1 (en) * 2000-08-21 2003-03-29 삼성에스디아이 주식회사 Electrode for lithium secondary batteries and lithium secondary batteries
JP2005251469A (en) * 2004-03-02 2005-09-15 Sanyo Electric Co Ltd Nonaqueous electrolyte battery
KR100659854B1 (en) * 2005-04-28 2006-12-19 삼성에스디아이 주식회사 Lithium secondary battery

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102934262A (en) * 2010-05-31 2013-02-13 日产自动车株式会社 Negative electrode for secondary battery, and process for production thereof
US9666858B2 (en) 2010-05-31 2017-05-30 Nissan Motor Co., Ltd. Negative electrode for secondary battery, and process for production thereof
CN107425174A (en) * 2010-05-31 2017-12-01 日产自动车株式会社 Secondary battery cathode and its manufacture method
CN101894937A (en) * 2010-07-02 2010-11-24 东莞新能源科技有限公司 Lithium ion battery and positive plate thereof
CN103531744A (en) * 2012-07-05 2014-01-22 苏州宝时得电动工具有限公司 Battery plate and electrode manufacturing method
CN112909228A (en) * 2021-01-13 2021-06-04 中科(马鞍山)新材料科创园有限公司 Modified negative pole piece and preparation method and application thereof
CN112909228B (en) * 2021-01-13 2022-05-24 中科(马鞍山)新材料科创园有限公司 Modified negative pole piece and preparation method and application thereof
CN117039194A (en) * 2023-08-29 2023-11-10 中创新航科技集团股份有限公司 Cylindrical battery

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Open date: 20081029