CN108400336A - A kind of high-safety polymer lithium ion battery anode glue size and preparation method thereof and lithium ion battery - Google Patents
A kind of high-safety polymer lithium ion battery anode glue size and preparation method thereof and lithium ion battery Download PDFInfo
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- CN108400336A CN108400336A CN201810221465.8A CN201810221465A CN108400336A CN 108400336 A CN108400336 A CN 108400336A CN 201810221465 A CN201810221465 A CN 201810221465A CN 108400336 A CN108400336 A CN 108400336A
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- lithium ion
- ion battery
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- lithium
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M10/42—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
-
- 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 present invention relates to a kind of high-safety polymer lithium ion battery anode glue size and preparation method thereof and lithium ion batteries, the anode sizing agent raw material includes positive active material, binder, conductive agent, solvent and ceramic additive, the ceramic additive is alundum (Al2O3) and/or titanium dioxide, additive amount >=1% of ceramic additive.The battery anode slurry of the present invention can reduce effective contact surface between cobalt acid lithium and electrolyte; to make the internal resistance of cell sharply increase; further increase the polarization of inside battery; battery is easier to reach protection voltage; the anti-over-charging performance of battery improves; the security performance of battery improves, and in the case where ensureing battery safety, while having high-energy density.
Description
Technical field：
The present invention relates to a kind of high-safety polymer lithium ion battery anode glue size and preparation method thereof and lithium ion batteries, belong to
In field of lithium ion battery.
Background technology：
With the update of consumer electronics product and the fast development of powered vehicle, energy storage device is towards more
High-energy density, longer service life, higher safety direction are developed.In all secondary cells, lithium ion battery tool
It standby the features such as high, high-specific-power, long circulation life and high-temperature behavior are good than energy, has obtained answering extensively in various fields
With.
Secondary lithium battery have passed through nearly development in 25 years, and energy density can accomplish that 700Wh/L is even higher,
But it is limited by material nature and process.After lithium ion battery energy density improves, its multiplying power is new
The performances such as energy, cycle life, high-temperature behavior and safety receive different degrees of inhibition.For current technology, cobalt acid
Lithium is the highest positive electrode of generally acknowledged energy density, and voltage can accomplish 4.45V.
But along with the higher and higher of lithium battery energy density, the safety problem that it is faced is also increasingly severeer,
The serious terminal for limiting lithium ion battery with high energy density uses.Such as：The global explosive incident of Samsung mobile phone in 2016, and
The explosive incident of 8 Plus series mobile phones of iphone.These experience are all warning us invariably, when we pursuit it is fast
While filling, grow continuation of the journey, we will also pay close attention to the security performance of product.
There are the report of certain methods and measure, such as Chinese patent literature for the improvement of lithium ion battery safety performance
201611121833.9 disclosing a kind of lithium ion battery high safety negative electrode slurry, come by adjusting the bonding agent of negative electrode slurry
Improve the security performance of negative electrode slurry, the lithium ion made can vividly stop exothermic reaction to ensure that battery makes at high temperature
Security performance in, but this method mainly improves cathode, meanwhile, this method plays effect for the protection overcharged
Fruit should be not obvious.
Chinese patent literature 201610586470.X discloses a kind of lithium ion battery, is set between battery inner core and shell
Insulating layer is set, electrolyte is can absorb and discharge, the electrolyte of its absorption is constantly discharged to supplement to inside battery, acts on battery
The insertion of lithium ion is moved out in charge and discharge cycles, is solved lithium ion battery and is asked due to a lack of cycle caused by electrolyte and safety
Topic.But the program may only applicable aluminum hull or box hat battery, meanwhile, be also unfavorable for high energy density cells making.
Chinese patent literature 201610294405.X discloses a kind of high security lithium ion battery, and the invention is mainly in group
It closes and sets one or more relief valves on the case lid of battery, and battery relief valve interior liquid halon extinguishing agent rapid evaporation
When, the temperature of battery pack can be reduced rapidly, and form low temperature inerting air insulated band inside and outside battery case or put out battery case
External burning things which may cause a fire disaster.The invention may be proper for power battery, is not suitable for the high energy density cells of 3C numbers.
Chinese patent literature 201110260368.8 discloses a kind of safety lithium ion cell, mainly battery-active object
It is middle to increase a kind of conductive agent, it is filled using the special conduction and overheats melted by heating in battery, losing electric conductivity leads to the resistance of active matter
Anti- increase, to improve the security performance of battery.But the high-temperature behavior of the battery can be very poor, the use environment of usual lithium battery
Temperature may reach 60 degree, or even can reach 80 degree；Therefore, there are prodigious security risks for the battery.
Invention content：
In view of the deficiencies of the prior art, a kind of high-safety polymer lithium ion battery anode glue size of present invention offer and its preparation
Method and lithium ion battery.
The Gen Ben of failure on fire occurs from battery for the present invention, by studying many times, has obtained the Gao An of the present invention
Full property anode of polymer lithium ion battery slurry.
The surface reason of failure on fire occurs for battery, be exactly nothing but battery PCM protection boards start to work before, battery is
Through being in thermal runaway state.And the usual operation voltage of PCM protection boards often 0.1V higher than cell voltage or so.Wherein I
PCM plates detected before action voltage can be equal to battery quiescent voltage add the charging time polarizing voltage.I.e.：
UPCM plates=UIt is static+UPolarization
In addition, according to battery heat production formula, i.e.,
Q=U*U/ R,
It, can be by improving battery preceding battery polarization out of control and preventing two kinds of means of short circuit of inside battery by above-mentioned analysis
To improve the security performance of battery.
The battery anode slurry of the present invention can reduce effective contact surface between cobalt acid lithium and electrolyte, to make battery
Internal resistance sharply increases, and further increases the polarization of inside battery, and battery is easier to reach protection voltage, the anti-over-charging of battery
Performance improves, and the security performance of battery improves.
Technical scheme is as follows：
A kind of high-safety polymer lithium ion battery anode glue size, the anode sizing agent raw material include positive active material, bonding
Agent, conductive agent, solvent and ceramic additive, the ceramic additive are alundum (Al2O3) and/or titanium dioxide, ceramics addition
Additive amount >=1% of agent.
According to currently preferred, the magnetisable material content inside ceramic additive is less than or equal to 50ppm, it is preferred that pottery
Magnetisable material content inside porcelain additive is less than or equal to 30ppm.
According to currently preferred, the water content of ceramic additive is less than or equal to 200ppm, it is preferred that ceramic additive
Water content is 50-100ppm.
According to currently preferred, the grain size of ceramic additive is less than or equal to 100nm, it is preferred that the grain of ceramic additive
Diameter is 40-60nm.
The ceramic additive of the present invention can hinder positive electrode active material and the direct of electrolyte to connect with coated positive electrode active material
It touches, reduces the negative reaction of inside battery.
According to currently preferred, the additive amount of ceramic additive accounts for the 1-5% of anode sizing agent total weight.
It is cobalt acid lithium according to currently preferred, described positive active material, binder is Kynoar, conductive agent
For conductive black, solvent is N-Methyl pyrrolidone.
A kind of preparation method of high-safety polymer lithium ion battery anode glue size, this method under low moisture environments into
Row, including step：
Binder, conductive agent, ceramic additive mixing step；
Stirring solvent mixing step is added；
Positive active material is added and is stirred step；
Testing size viscosity, solid content, sifting step.
It is less than 20% according to the humidity of currently preferred, described low moisture environments.
According to currently preferred, it is added in stirring solvent mixing step, speed of agitator 700-900HZ, mixing time
1-3h。
According to currently preferred, positive active material is added and is stirred in step, speed of agitator 1100-
1400HZ, mixing time 1-3h.
According to currently preferred, in testing size viscosity, solid content, sifting step, viscosity meet 4000 Pa.s ~
13000Pa.s；Solid content is 50% ~ 80%.
A kind of high-safety polymer lithium ion battery, including lithium-ion electric core and PCM protection boards, lithium-ion electric core include
Lithium ion cell positive, negative electrode of lithium ion battery, lithium ion battery separator, lithium-ion battery electrolytes, lithium ion cell polar ear,
And casing of lithium ion battery, the lithium ion cell positive are to be coated uniformly on aluminium foil to be made using battery anode slurry,
Coated weight is 16mg/cm2~25 mg/cm2。
According to currently preferred, negative electrode active material capacity is more than positive active material capacity.
According to currently preferred, described negative electrode of lithium ion battery, which includes active material, cementability, conduction
Agent, copper foil.
Cathode is carried out by the conventional of this field.
Currently preferred, the lithium ion battery separator includes matrix and is attached at least side table of described matrix
The coating in face, wherein contain ceramic particle and binder in the coating, the thickness of coating is 1~10 μm, basis material PE
Or PP, the porosity of barrier film base material is 35~60%, aperture 30-500nm.
Currently preferred, the lithium-ion battery electrolytes are made of solvent, additive and lithium salts；The solvent is carbon
One in dimethyl phthalate DMC, diethyl carbonate DEC, methyl ethyl ester EMC, propene carbonate PC or ethylene carbonate EC
Kind or two or more mixing；The additive is vinylene carbonate VC, benzene sulfone PS, vinylethylene carbonate VEC or fluoro
One or more of ethylene carbonate FEC is mixed；The lithium salts is one kind in LiPF6, LiBF4 or LiClO4
Or two or more mixing.
Currently preferred, described lithium ion cell polar ear, lug include positive aluminium pole ears and cathode nickel lug.
Currently preferred, the shell of the casing of lithium ion battery is formed by nylon layer, aluminium layer and PP layers of polymer.
Beneficial effects of the present invention：
1, battery anode slurry of the invention can reduce effective contact surface between cobalt acid lithium and electrolyte, to make in battery
Resistance sharply increases, and further increases the polarization of inside battery, and battery is easier to reach protection voltage, the anti-over-charging of battery
It can improve, the security performance of battery improves.
2, battery anode slurry of the invention is in the case where ensureing battery safety, while having high-energy density.
3, after the nano level ceramics of addition of the invention, guarantor's liquid measure of battery increases, and pole piece effect of impregnation can be more preferable；
4, cobalt acid lithium reduces the oxidation of electrolyte, can improve the gram volume of electric positive electrode；
5, meeting of the invention effectively reduces loss of the electrolyte on cobalt acid lithium surface, and cycle performance of battery can be improved.
Description of the drawings：
Fig. 1 is the structural model figure after ceramic coatings cobalt acid lithium in anode sizing agent；
Fig. 2 is under the conditions of overcharging, and ceramic coatings cobalt acid lithium area ratio increases illustraton of model；
Specific implementation mode：
Below by specific embodiment, the present invention will be further described, but not limited to this.
The raw material used in embodiment is conventional commercial product.
Embodiment 1：
A kind of preparation method of high-safety polymer lithium ion battery anode glue size, is as follows：
1）In low humidity room of the humidity less than 20%, the PVDF cementabilities, the conductive black of 15g and the ceramic powder of 10g of 20g are taken
Material is put into agitator tank；
2）420g NMP solvents are added and are stirred 2h using the rotating speed of 800HZ；
3）955g cobalt acid lithium materials are added into agitator tank again, 2h is stirred using the rotating speed of 1200HZ；
4）After the completion of mixing, the viscosity and solid content of testing size；
5）It is sieved to made slurry using the sieve of 200 mesh, removes bulky grain；
Embodiment 2：
A kind of preparation method of high-safety polymer lithium ion battery anode glue size, is as follows：
1）In low humidity room of the humidity less than 20%, the PVDF cementabilities, the conductive black of 15g and the ceramic powder of 20g of 20g are taken
Material is put into agitator tank；
2）420g NMP solvents are added and are stirred 2h using the rotating speed of 800HZ；
3）945g cobalt acid lithium materials are added into agitator tank again, 2h is stirred using the rotating speed of 1200HZ；
4）After the completion of mixing, the viscosity and solid content of testing size；
5）It is sieved to made slurry using the sieve of 200 mesh, removes bulky grain；
Embodiment 3：
A kind of preparation method of high-safety polymer lithium ion battery anode glue size, is as follows：
1）In low humidity room of the humidity less than 20%, the PVDF cementabilities, the conductive black of 15g and the ceramic powder of 30g of 20g are taken
Material is put into agitator tank；
2）420g NMP solvents are added and are stirred 2h using the rotating speed of 800HZ；
3）935g cobalt acid lithium materials are added into agitator tank again, 2h is stirred using the rotating speed of 1200HZ；
4）After the completion of mixing, the viscosity and solid content of testing size；
5）It is sieved to made slurry using the sieve of 200 mesh, removes bulky grain；
Embodiment 4：
A kind of preparation method of high-safety polymer lithium ion battery anode glue size, is as follows：
1）In low humidity room of the humidity less than 20%, the PVDF cementabilities, the conductive black of 15g and the ceramic powder of 50g of 20g are taken
Material is put into agitator tank；
2）420g NMP solvents are added and are stirred 2h using the rotating speed of 800HZ；
3）915g cobalt acid lithium materials are added into agitator tank again, 2h is stirred using the rotating speed of 1200HZ；
4）After the completion of mixing, the viscosity and solid content of testing size；
5）It is sieved to made slurry using the sieve of 200 mesh, removes bulky grain；
Comparative example 1
A kind of preparation method of anode of polymer lithium ion battery slurry the difference is that, is free of with embodiment 1 in the slurry
There is ceramic additive.
Comparative example 2
A kind of preparation method of anode of polymer lithium ion battery slurry, with embodiment 1 the difference is that, it is ceramic in the slurry
The additive amount of additive is 5g.
Experimental example：
By embodiment 1-4 and the anode sizing agent of comparative example 2 uniformly be coated in aluminium foil surface on be made positive electrode, then with lithium
Ion battery cathode, lithium ion battery separator, lithium-ion battery electrolytes, lithium ion cell polar ear and casing of lithium ion battery
Assembling, lithium ion battery is made by battery production production process.
Lithium ion battery obtained above is carried out under the conditions of 3C/5V to overcharge test, test result see the table below shown in 1:
Claims (10)
1. a kind of high-safety polymer lithium ion battery anode glue size, which includes positive active material, glues
Agent, conductive agent, solvent and ceramic additive are tied, the ceramic additive is alundum (Al2O3) and/or titanium dioxide, and ceramics add
Add additive amount >=1% of agent.
2. high-safety polymer lithium ion battery anode glue size according to claim 1, which is characterized in that ceramics addition
Magnetisable material content inside agent is less than or equal to 50ppm, it is preferred that the magnetisable material content inside ceramic additive is less than or equal to
30ppm。
3. high-safety polymer lithium ion battery anode glue size according to claim 1, which is characterized in that ceramics addition
The water content of agent is less than or equal to 200ppm, it is preferred that the water content of ceramic additive is 50-100ppm.
4. high-safety polymer lithium ion battery anode glue size according to claim 1, which is characterized in that ceramics addition
The grain size of agent is less than or equal to 100nm, it is preferred that the grain size of ceramic additive is 40-60nm.
5. high-safety polymer lithium ion battery anode glue size according to claim 1, which is characterized in that ceramics addition
The additive amount of agent accounts for the 1-5% of anode sizing agent total weight；The positive active material is cobalt acid lithium, and binder is polyvinylidene fluoride
Alkene, conductive agent are conductive black, and solvent is N-Methyl pyrrolidone.
6. a kind of preparation method of high-safety polymer lithium ion battery anode glue size, this method carry out under low moisture environments,
Including step：
Binder, conductive agent, ceramic additive mixing step；
Stirring solvent mixing step is added；
Positive active material is added and is stirred step；
Testing size viscosity, solid content, sifting step.
7. the preparation method of high-safety polymer lithium ion battery anode glue size according to claim 6, feature exist
In the humidity of the low moisture environments is less than 20%.
8. the preparation method of high-safety polymer lithium ion battery anode glue size according to claim 6, feature exist
In, in addition stirring solvent mixing step, speed of agitator 700-900HZ, mixing time 1-3h；Positive active material is added to stir
It mixes in mixing step, speed of agitator 1100-1400HZ, mixing time 1-3h；Testing size viscosity, solid content, sifting step
In, viscosity meets 4000 Pa.s ~ 13000Pa.s；Solid content is 50% ~ 80%.
9. a kind of high-safety polymer lithium ion battery, including lithium-ion electric core and PCM protection boards, lithium-ion electric core include lithium
Ion battery anode, negative electrode of lithium ion battery, lithium ion battery separator, lithium-ion battery electrolytes, lithium ion cell polar ear and
Casing of lithium ion battery, the lithium ion cell positive are to be coated uniformly on aluminium foil to be made using battery anode slurry, are applied
The amount of covering is the mg/cm2 of 16mg/cm2 ~ 25；Negative electrode active material capacity is more than positive active material capacity.
10. high-safety polymer lithium ion battery according to claim 9, which is characterized in that the lithium-ion electric
Pond cathode, the cathode include active material, cementability, conductive agent, copper foil；The lithium ion battery separator includes matrix and attached
It in the coating of an at least side surface for described matrix, wherein contain ceramic particle and binder, the thickness of coating in the coating
Degree is 1~10 μm, and basis material is PE or PP, and the porosity of barrier film base material is 35~60%, aperture 30-500nm；
The lithium-ion battery electrolytes are made of solvent, additive and lithium salts；The solvent be dimethyl carbonate DMC,
One or more of diethyl carbonate DEC, methyl ethyl ester EMC, propene carbonate PC or ethylene carbonate EC
Mixing；The additive is vinylene carbonate VC, benzene sulfone PS, vinylethylene carbonate VEC or fluorinated ethylene carbonate FEC
One or more of mixing；The lithium salts is one or more of LiPF6, LiBF4 or LiClO4 mixed
It closes；The lithium ion cell polar ear, lug include positive aluminium pole ears and cathode nickel lug；The casing of lithium ion battery
Shell formed by nylon layer, aluminium layer and PP layers of polymer.
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| CN201810221465.8A CN108400336A (en) | 2018-03-17 | 2018-03-17 | A kind of high-safety polymer lithium ion battery anode glue size and preparation method thereof and lithium ion battery |
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| CN201810221465.8A CN108400336A (en) | 2018-03-17 | 2018-03-17 | A kind of high-safety polymer lithium ion battery anode glue size and preparation method thereof and lithium ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190283A (en) * | 2019-06-18 | 2019-08-30 | 深圳鸿鹏新能源科技有限公司 | Negative electrode slurry and its preparation method and application |
| CN114171779A (en) * | 2021-11-22 | 2022-03-11 | 中国电子科技集团公司第十八研究所 | High-safety lithium ion battery and preparation method thereof |
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| CN100433439C (en) * | 2002-12-23 | 2008-11-12 | 3M创新有限公司 | Cathode composition for rechargeable lithium battery |
| CN202888310U (en) * | 2012-10-31 | 2013-04-17 | 东莞市金源电池科技有限公司 | Cell assembly structure of polymer lithium battery pack |
| CN103456908A (en) * | 2012-05-28 | 2013-12-18 | 万向电动汽车有限公司 | High security diaphragm and high capacity lithium ion power battery using high security diaphragm |
| CN203521496U (en) * | 2013-09-04 | 2014-04-02 | 厦门钨业股份有限公司 | Apple-shaped large-power polymer lithium battery |
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2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100433439C (en) * | 2002-12-23 | 2008-11-12 | 3M创新有限公司 | Cathode composition for rechargeable lithium battery |
| CN103456908A (en) * | 2012-05-28 | 2013-12-18 | 万向电动汽车有限公司 | High security diaphragm and high capacity lithium ion power battery using high security diaphragm |
| CN202888310U (en) * | 2012-10-31 | 2013-04-17 | 东莞市金源电池科技有限公司 | Cell assembly structure of polymer lithium battery pack |
| CN203521496U (en) * | 2013-09-04 | 2014-04-02 | 厦门钨业股份有限公司 | Apple-shaped large-power polymer lithium battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190283A (en) * | 2019-06-18 | 2019-08-30 | 深圳鸿鹏新能源科技有限公司 | Negative electrode slurry and its preparation method and application |
| CN114171779A (en) * | 2021-11-22 | 2022-03-11 | 中国电子科技集团公司第十八研究所 | High-safety lithium ion battery and preparation method thereof |
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Application publication date: 20180814 |