CN106848383A - A kind of lithium ion battery of high security and preparation method thereof - Google Patents
A kind of lithium ion battery of high security and preparation method thereof Download PDFInfo
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- CN106848383A CN106848383A CN201710129249.6A CN201710129249A CN106848383A CN 106848383 A CN106848383 A CN 106848383A CN 201710129249 A CN201710129249 A CN 201710129249A CN 106848383 A CN106848383 A CN 106848383A
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- lithium ion
- organic polymer
- negative plate
- ion battery
- polymer coating
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/02—Details
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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
- H01M10/058—Construction or manufacture
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of lithium ion battery of high security and preparation method thereof, chemically inert organic polymer coating is coated on the negative plate for having prepared, the organic polymer coating is water insoluble, the fusing point of the organic polymer coating is 90 110 DEG C, occur because overcharging in lithium ion battery, heavy impact, thermal shock, short circuit, acupuncture, caused by the destructive collision such as extruding during the thermal runaway of internal short-circuit of battery, polyethylene nanoparticle coating can melt the clad to form negative plate surface, a diaphragm is formed on negative plate surface, the contact short circuit of positive plate and negative plate can effectively be completely cut off, inlaying and separating out for lithium metal ion can effectively be prevented, and then can be risen with the further temperature of the dissolving of inhibitory activity material and thermal runaway, the whole security performance of battery core can be obviously improved.
Description
Technical field
Technical field of lithium ion of the present invention, and in particular to a kind of lithium ion battery of high security and its preparation side
Method.
Background technology
Lithium ion battery has been widely used all trades and professions, with application field popularization and experience requirement increasingly
Height, terminal client requires that also no maturation can completely improve lithium in also more and more higher, current industry to the security performance of lithium battery
The products such as ion battery security performance.The mobile phone explosive incident for once occurring, although specific explosion cause do not investigate it is clear, but
Analysis in the industry is likely to the safety coefficient of its high-energy-density lithium battery for using and does not meet the requirement institute of related International Certification
Cause.
Lithium battery product with battery energy density more and more higher, using to material also become closer to the limit, such as protect
The base material of protective function --- barrier film, more with thinner, the barrier film commercially supplied at present is most thin 7~10um, and this can cause electricity
The safety coefficient in pond can drastically decline, therefore the simple safe bearing capacity by positive and negative pole material itself goes support battery overall
Security is very difficult.For the safety problem of lithium battery, most of present battery core manufacturer is by using barrier film
The metal materials such as coated ceramic layer, positive pole addition nickel, manganese are doped and Copper Foil/aluminium foil surface carries out coating processing, uses stone
The modes such as black alkene, lithium titanate carry out safety improvement.Above means respectively have feature, also play certain safety improvement effect.But
It is that the security performance of battery still cannot meet demand, therefore in the urgent need to a kind of lithium ion battery of high safety performance.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of security lithium ion battery higher and preparation method thereof.
The technical solution used in the present invention is:
A kind of lithium ion battery, including negative plate and positive plate, are coated with chemically inert organic poly- on the negative plate
Compound coating, the organic polymer coating is water insoluble, and the fusing point of the organic polymer coating is 90-110 DEG C, described to have
When lithium ion battery occurs thermal runaway, fusing forms the clad on negative plate surface to machine polymer coating, isolation positive plate and
The contact short circuit of negative plate.
Some preferred embodiment in, the organic polymer coating be nanoparticle coating.
Such scheme preferred embodiment in, the nano particle be polyethylene, polypropylene, low density polyethylene
Alkene, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, haloflex, polyvinyl chloride,
Any one in TPUE.
Such scheme preferred embodiment in, the particle diameter of the nano particle is 3-30nm.
Some preferred embodiment in, the negative plate include collector, the carbon-coating being coated on collector, it is described
Organic polymer coating is coated on the surface of the carbon-coating.
Such scheme preferred embodiment in, the carbon-coating be graphite linings, hard carbon material layer or soft carbon material layer
In any one.
Some preferred embodiment in, the organic polymer coating thickness be 1-5 μm.
Present invention also offers a kind of preparation method of lithium ion battery as described above, including negative plate is prepared, then
The step of coating one layer of organic polymer coating on negative plate, the fusing point of the organic polymer coating is 90-110 DEG C.
Some preferred embodiment in, it is described on negative plate coat one layer of organic polymer coating the step of it is specific
For:Nano particle is scattered in binder solution, latex solution is configured to, then latex solution is coated in negative plate surface,
Dry.
Such scheme preferred embodiment in, the bonding agent is butadiene-styrene rubber, sodium carboxymethylcellulose, poly- inclined
Any one in PVF or gelatin.
Such scheme preferred embodiment in, it is described one layer of organic polymer coating is coated on negative plate to use
Be any one coating processes in extrusion coated, transfer coated, spraying.
The beneficial effects of the invention are as follows:
The invention provides a kind of lithium ion battery of high security and preparation method thereof, in the negative plate for having prepared
One layer of organic polymer coating of upper coating, organic polymer coating does not have complete bag is formed on negative plate under original state
Coating, the fusing point of the organic polymer coating is 90-110 DEG C, is occurred because overcharging in lithium ion battery, heavy impact, Re Chong
Hit, short circuit, acupuncture, extruding etc. is destructive collide caused by internal short-circuit of battery thermal runaway when, organic polymer coating can melt
Change forms the clad on negative plate surface, and a diaphragm is formed on negative plate surface, can effectively completely cut off positive plate and negative plate
Contact short circuit, can effectively prevent inlaying and separating out for lithium metal ion, and then can be lost with the dissolving of inhibitory activity material and heat
The further temperature of control rises, and can be obviously improved the whole security performance of battery core.
Brief description of the drawings
Fig. 1 is the schematic cross-section of negative plate.
Fig. 2 is the electron microscope before the fusing of polyethylene nanoparticle coating.
Fig. 3 is the hot-fluid spirogram of polyethylene nanoparticle coating.
Fig. 4 is the electron microscope after the fusing of polyethylene nanoparticle coating.
Fig. 5 is performance state diagram of the negative plate after acupuncture is carried out.
Specific embodiment
Embodiment 1:
It is first according to conventional anode plate for lithium ionic cell preparation technology and prepares negative plate, negative plate includes collector, applies
It is overlying on the carbon-coating on collector, the carbon-coating is any one in graphite linings, hard carbon material layer or soft carbon material layer, including then
Take nano particle to be scattered in binder solution, be configured to latex solution, the fusing point of the nano particle is 90-110 DEG C, described
Nano particle can be dissaving polymer or dendritic, it is preferable that the nano particle is polyethylene, polypropylene, low
Density polyethylene, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, haloflex,
Any one in polyvinyl chloride, TPUE, the nano particle is polyethylene nanometer in the present embodiment
Grain, the bonding agent is any one in butadiene-styrene rubber, sodium carboxymethylcellulose, Kynoar or gelatin, in the present embodiment
Described in bonding agent be butadiene-styrene rubber (SBR), then using extrusion coated, transfer coated, any one coating processes general such as spraying
Latex solution is coated in the carbon-coating surface of negative plate, dries, that is, obtain nanoparticle coating, and the fusing point of nanoparticle coating is
The fusing point of nano particle, will not change substantially, and the schematic cross-section of the negative plate for obtaining is as shown in figure 1, negative plate includes
Collector 1 and the carbon-coating 2 being coated in the upper and lower surface of collector 1, the carbon-coating 2 is graphite linings, the carbon in the present embodiment
The surface of layer 2 is coated with polyethylene nanoparticle coating 3, and the thickness of the polyethylene nanoparticle coating 3 is 1 μm.
The polyethylene nanoparticle coating prepared using scanning electron microscopic observation, it was observed that electron microscope as shown in Fig. 2
It can be seen that polyethylene nano-particle diameter has space, the particle diameter of the polyethylene nano particle is 3-30nm.The poly- second
The fusing point of alkene nanoparticle coating is 90 DEG C -110 DEG C, and the fusing point of the polyethylene nano particle for being used in the present embodiment is as schemed
It it is 104 DEG C shown in 3.
Using the negative plate by above-mentioned coating, cobalt acid lithium/graphite cell, positive pole are prepared according still further to conventional preparation technology
In electrode proportioning, cobalt acid lithium accounts for 96%, and its positive pole uses safety-type cobalt acid lithium material, its lithium titanate covering amount 0.5%;Negative electricity
In the proportioning of pole, graphite accounts for 96%;Barrier film uses routine PP/PE/PP three-layer membranes, and electrolyte is routine business electrolyte, system
It is standby to obtain lithium ion battery cell, battery core capacity 3.8Ah.Occur because overcharging in lithium ion battery, it is heavy impact, thermal shock, short
Caused by the destructive collision such as road, acupuncture, extruding during the thermal runaway of internal short-circuit of battery, temperature is close to close to or up fusing point
When, polyethylene nanoparticle coating can melt the clad to form negative plate surface, and a diaphragm is formed on negative plate surface,
The contact short circuit of positive plate and negative plate can effectively be completely cut off, inlaying and separating out, Jin Erke for lithium metal ion can be effectively prevented
Risen with the further temperature of the dissolving of inhibitory activity material and thermal runaway, the whole security performance of battery core can be obviously improved.Adopt
With state after polyethylene nanoparticle coating high temperature melting described in scanning electron microscopic observation, it was observed that electron microscope as shown in figure 4, can
A complete clad is formd to see that polyethylene nano particle has melted.If not using polyethylene nano particle
And common polyethylene coating is simply used, because polyethylene particle is big, the uniformity is poor, coats the film for being formed in high temperature melting mistake
Cheng Zhong, polyethylene can be assembled, and easily form cavity, it is impossible to form complete clad, it is difficult to completely cut off positive plate and negative pole
The contact short circuit of piece, it is impossible to control the further thermal runaway of battery, it is impossible to lift the security performance of battery core.
Comparative example 1:
Using conventional graphite cathode piece, i.e. the not applying coating on graphite prepares cobalt according still further to conventional preparation technology
Sour lithium/graphite cell, in anode electrode proportioning, cobalt acid lithium accounts for 96%, and its positive pole uses safety-type cobalt acid lithium material, its lithium titanate
Covering amount 0.5%;In negative electrode proportioning, graphite accounts for 96%;Barrier film uses routine PP/PE/PP three-layer membranes, and electrolyte is normal
Rule commercialization electrolyte, prepares lithium ion battery cell, battery core capacity 3.8Ah.
The contrast experiment of embodiment 1 and comparative example 1:The lithium ion battery that Example 1 and comparative example 1 are prepared respectively
Battery core carries out following security performance test:1st, leptoprosopy extruding:Fully charged embodiment 1 and the battery of comparative example 1, respectively take 10pcs,
Battery core side upright is positioned between two parallel-plates, 17.2MPa, pressurize 1min, then release of pressure is gradually forced into, 1h is observed.Electricity
Pond is not on fire, do not explode as qualified.2nd, test is overcharged:By embodiment 1 and the battery core of comparative example 1,10pcs is respectively taken, battery core is existed
Under 23 ± 5 DEG C of states, battery core is first discharged into 3.0V, 5V is charged to the electric current of 3C multiplying powers, allowed electric current to decline under certain voltage and connect
Closely it is 0A, monitoring battery temperature change, when temperature drop is lower than peak value about 10 DEG C, stops experiment.Battery core is not on fire, do not explode
As pass through.3rd, 150 DEG C of hot tanks:Fully charged embodiment 1 and the battery of comparative example 1, respectively take 10pcs, and battery is positioned over into hot tank
In, temperature is risen to 150 DEG C ± 2 DEG C and is incubated 10min with the speed of (5 DEG C ± 2 DEG C)/min, records battery surface temperature, record
Experimental phenomena, battery is not on fire, not exploding to be considered as passes through.4th, acupuncture:Fully charged embodiment 1 and the battery of comparative example 1, respectively take
10pcs, with 3mm needle-penetration batteries, thorn speed is 50mm/s, records battery surface temperature, records experimental phenomena, battery is on fire,
Do not explode to be considered as and pass through.5th, short circuit:Fully charged embodiment 1 and the battery of comparative example 1, respectively take 10pcs, and battery core positive pole is turned into nickel
Afterwards, both positive and negative polarity, monitoring battery temperature change, when temperature drop is lower than peak value about are connected using the different internal resistance wires of 30,45m Ω
At 10 DEG C, stop experiment.Battery core is not on fire, does not explode, and surface temperature is test passes no more than 150 DEG C.
The security performance test result for obtaining is as shown in table 1, it can be seen that prepared using the method for the invention
Lithium ion battery its security performance is obviously improved, and performance state such as Fig. 5 institute of the gained battery of embodiment 1 after acupuncture is carried out
Show, it can be seen that pole piece is short-circuited calcination, after then polyethylene nano particle melts and to form clad, calcination point after acupuncture
Without diffusion, only one round dot, the thermal runaway of battery has obtained effective control.Further illustrate of the present invention in negative pole
Coating polyethylene nanoparticle coating can form a diaphragm after high temperature melting on negative plate surface on piece, and isolation is just
The contact short circuit of negative pole, can effectively improve the security performance of battery.
The security performance test result of the embodiment 1 of table 1 and the battery of comparative example 1
Embodiment 2:
It is first according to conventional anode plate for lithium ionic cell preparation technology and prepares negative plate, negative plate includes collector, applies
It is overlying on the carbon-coating on collector, the carbon-coating is any one in graphite linings, hard carbon material layer or soft carbon material layer, including then
The nano particle for taking ethylene-vinyl acetate copolymer is scattered in binder solution, is configured to latex solution, in the present embodiment
Described in bonding agent be sodium carboxymethylcellulose, then using extrusion coated, transfer coated, any one coating processes general such as spraying
Latex solution is coated in the carbon-coating surface of negative plate, dries, that is, obtain ethylene-vinyl acetate copolymer coating, and the ethene-
The thickness of vinyl acetate co-polymer coating is 5~10 μm.The lithium-ion electric that Example 2 and comparative example 1 are prepared respectively
Pond battery core carries out following security performance test:Obtain experimental result as shown in table 2.
The security performance test result of the embodiment 2 of table 2 and the battery of comparative example 1
Claims (10)
1. a kind of lithium ion battery, including negative plate and positive plate, it is characterised in that be coated with chemical inertness on the negative plate
Organic polymer coating, the organic polymer coating is water insoluble, and the fusing point of the organic polymer coating is 90-110
DEG C, when lithium ion battery occurs thermal runaway, fusing forms the clad on negative plate surface, isolation to the organic polymer coating
The contact short circuit of positive plate and negative plate.
2. lithium ion battery according to claim 1, it is characterised in that the organic polymer coating is that nano particle is applied
Layer.
3. lithium ion battery according to claim 2, it is characterised in that the nano particle is polyethylene, polypropylene, low
Density polyethylene, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, haloflex,
Any one in polyvinyl chloride, TPUE.
4. lithium ion battery according to claim 2, it is characterised in that the particle diameter of the nano particle is 3-30nm.
5. the lithium ion battery according to claim any one of 1-3, it is characterised in that the negative plate include collector,
The carbon-coating on collector is coated on, the organic polymer coating is coated on the surface of the carbon-coating.
6. the lithium ion battery according to claim any one of 1-3, it is characterised in that the organic polymer coating thickness
It is 1-5 μm.
7. the preparation method of the lithium ion battery described in a kind of any one of claim 1-6, it is characterised in that including preparing negative pole
Piece, then on negative plate the step of one layer of organic polymer coating of coating, the fusing point of the organic polymer coating is 90-
110℃。
8. the preparation method of lithium ion battery according to claim 7, it is characterised in that described that is coated on negative plate
The step of layer organic polymer coating, is specially:Nano particle is scattered in binder solution, latex solution is configured to, then will
Latex solution is coated in negative plate surface, dries.
9. the preparation method of lithium ion battery according to claim 8, it is characterised in that the bonding agent is butylbenzene rubber
Any one in glue, sodium carboxymethylcellulose, Kynoar or gelatin.
10. the preparation method of lithium ion battery according to claim 8 or claim 9, it is characterised in that described to be applied on negative plate
Cover any one coating processes during one layer of organic polymer coating uses extrusion coated, transfer coated, spraying.
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Cited By (21)
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CN108075101A (en) * | 2017-12-11 | 2018-05-25 | 中航锂电技术研究院有限公司 | Anode plate for lithium ionic cell with Thermal shutdown coating |
CN108461693A (en) * | 2018-03-31 | 2018-08-28 | 广东天劲新能源科技股份有限公司 | A kind of preparation method improving lithium ion battery thermal shock and short-circuit diaphragm |
CN109671981A (en) * | 2018-12-19 | 2019-04-23 | 清远佳致新材料研究院有限公司 | The application of polyurethane and/or polyoxypropyleneglycol, electrolyte, battery cathode, battery diaphragm, battery, electric vehicle |
EP3591738A1 (en) * | 2018-07-03 | 2020-01-08 | Samsung SDI Co., Ltd. | Electrode for rechargeable lithium battery, and rechargeable lithium battery including the same |
CN111326739A (en) * | 2020-02-28 | 2020-06-23 | 浙江克能新能源科技有限公司 | Soft-package lithium manganate battery and manufacturing method thereof |
CN111564661A (en) * | 2020-06-24 | 2020-08-21 | 天能帅福得能源股份有限公司 | High-safety lithium ion battery |
EP3734707A1 (en) * | 2019-05-03 | 2020-11-04 | Samsung SDI Co., Ltd. | Rechargeable lithium battery |
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CN112889164A (en) * | 2020-04-23 | 2021-06-01 | 宁德时代新能源科技股份有限公司 | Lithium metal battery, preparation method thereof, device containing lithium metal battery and negative pole piece |
CN113363604A (en) * | 2021-06-07 | 2021-09-07 | 芜湖天弋能源科技有限公司 | Method for improving needling performance of lithium ion battery and high-safety lithium ion battery |
CN113394406A (en) * | 2021-05-31 | 2021-09-14 | 惠州锂威电子科技有限公司 | Current collector, electrode plate and lithium ion battery |
CN114175348A (en) * | 2019-07-24 | 2022-03-11 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
CN114824259A (en) * | 2021-01-27 | 2022-07-29 | 郑州宇通集团有限公司 | Lithium ion battery composite positive plate, preparation method thereof and lithium ion battery |
US11430987B2 (en) | 2018-12-12 | 2022-08-30 | Samsung Sdi Co., Ltd. | Electrode and a rechargeable lithium battery including the electrode |
US11508992B2 (en) | 2019-05-03 | 2022-11-22 | Samsung Sdi Co. Ltd. | Rechargeable lithium battery |
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US11705585B2 (en) | 2018-07-03 | 2023-07-18 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
CN117374438A (en) * | 2023-12-08 | 2024-01-09 | 中国第一汽车股份有限公司 | Negative electrode plate, preparation method thereof and lithium ion battery comprising negative electrode plate |
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US11522183B2 (en) | 2019-05-03 | 2022-12-06 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
US11522185B2 (en) | 2019-05-03 | 2022-12-06 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
US11508992B2 (en) | 2019-05-03 | 2022-11-22 | Samsung Sdi Co. Ltd. | Rechargeable lithium battery |
US11515523B2 (en) | 2019-05-03 | 2022-11-29 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
US11658287B2 (en) | 2019-05-03 | 2023-05-23 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
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