CN107170987A - A kind of preparation method of the positive plate of cell positive material and the use cell positive material - Google Patents
A kind of preparation method of the positive plate of cell positive material and the use cell positive material Download PDFInfo
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- CN107170987A CN107170987A CN201710090297.9A CN201710090297A CN107170987A CN 107170987 A CN107170987 A CN 107170987A CN 201710090297 A CN201710090297 A CN 201710090297A CN 107170987 A CN107170987 A CN 107170987A
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- additive
- silicones
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- positive material
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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
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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
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- Chemical Kinetics & Catalysis (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of preparation method of cell positive material and positive plate using the cell positive material, the cell positive material includes positive electrode active materials, conductive agent, binding agent and functional additive, and the mass ratioes of four kinds of components is 95:2.5:1.5:1.The functional additive includes inorganic additive and organic additive.The functional additive is added in positive plate, both the possibility burnt or exploded as caused by temperature abruptly increase can have been reduced, the security performance of battery is improved, while avoiding additive directly and cathode contact, it is to avoid the capacitance loss brought by additive and negative pole compatibility.In addition, being used in mixed way using organic additive and inorganic additive substep, additive can not only be enable to be well mixed with positive electrode, conductive agent, binding agent, and the two can act synergistically, and further improve fire resistance, improve the safety of acupuncture performance of battery.
Description
Technical field
The present invention relates to field of lithium ion battery material, particularly a kind of cell positive material and the anode material is used
The preparation method of the positive plate of material.
Background technology
Lithium ion battery has the advantage such as operating high voltage, high specific energy, long circulation life, high self-discharge rate, pollution-free, existing
The miniaturized electronics such as mobile phone, portable computer, digital product are widely used in, and it is dynamic in electric automobile and mixing
Wide application prospect and powerful growth momentum are shown on the vehicles such as power automobile.
Lithium ion battery is mainly made up of positive and negative pole material, barrier film and electrolyte.The safety problem of lithium battery is current reality
One big bottleneck of border application, when high rate charge-discharge, inside battery, which produces various electrochemical reactions, causes internal temperature of battery
Gentle pressure holding is of continuing rising high and causes battery easily thermal runaway, or even causes the burning and blast of battery.But fundamentally to solve
The certainly security performance of lithium ion battery, it is necessary to optimize the performance of used in battery material, use the battery material of high safety performance.
The measure of traditional raising lithium battery security performance is included using current protection plate, limitation battery operating voltage, electricity
Flame-retardant additive is added in solution liquid, the modes such as PTC are set in inside battery, though these modes can improve electricity to a certain extent
Pond security performance, but certain negative effect is produced to battery, such as current protection plate is directed to external short-circuit of battery, to battery
Internal short-circuit is helpless；The performance of battery energy density is also limit while limitation operating voltage；Resistance is added in electrolyte
Combustion additive can reduce electrolytic conductivity and cause the internal resistance of cell to increase；PTC is internally set then to be produced to battery design certain
Influence etc..Meanwhile, these safeguard procedures lack enough protective actions for typical outside batteries acupuncture situation.Due to pin
Direct short-circuit occurs for inside battery in the case of thorn, and electric current increases suddenly causes internal temperature of battery abruptly increase, adds battery catches fire blast
Danger, therefore higher requirement of shelter is proposed to battery acupuncture.
The content of the invention
In view of this, the invention provides a kind of cell positive material of safety of acupuncture performance for improving positive plate and make
With the preparation method of the positive plate of the cell positive material, to solve above-mentioned technical problem.
A kind of cell positive material, it includes positive electrode active materials, and conductive agent, binding agent and functional additive should
The mass ratio of four kinds of components is 95:2.5:1.5:1, the functional additive includes inorganic additive and organic additive, institute
It is at least one of boric acid, borax, molybdenum oxide, zinc oxide, tin oxide and iron oxide or several mixing to state inorganic additive
Thing, the organic additive is that the silicones of silicon oxygen bond and/or silicon-carbon bonds and cracking carbon-coating can be cracked to form in high temperature,
The silicones can decomposite amino or fluorine, the silicon oxygen bond and/or silicon-carbon bonds and inorganic additive of the silicones in cracking
Inorganic oxygen barrier heat-insulating protective layer is formed to improve fire resistance.
Further, the positive electrode active materials be cobalt acid lithium, LiMn2O4, LiFePO 4, lithium nickelate in one kind or
It is several.
Further, the conductive agent is natural flake graphite, micro crystal graphite or conductive carbon black.
Further, the binding agent is one kind or several in Kynoar, polytetrafluoroethylene (PTFE), CMC
The mixture planted.
Further, the silicones be methyl silicon resin, methylbenzene silicones, poly- methyl silicon resin, amino silicone,
At least one of fluorine silicon resin.
Further, the silicones is amino silicone or fluorine silicon resin.
Further, inorganic additive accounts for the 10% of the gross mass of the functional additive in the functional additive
~30%.
A kind of preparation method of the positive plate of use cell positive material, it comprises the following steps：
S1：Positive electrode active materials, conductive agent, binding agent and functional additive are pressed to the mass ratio of four kinds of components
For 95:2.5:1.5:1 is got the raw materials ready, and the functional additive includes inorganic additive and organic additive, described inorganic to add
It is described to have plus agent is at least one of boric acid, borax, molybdenum oxide, zinc oxide, tin oxide and iron oxide or several mixtures
Machine additive is that the silicones of silicon oxygen bond and/or silicon-carbon bonds and cracking carbon-coating, the silicon tree can be cracked to form in high temperature
Fat can decomposite amino or fluorine in cracking, and silicon oxygen bond and/or silicon-carbon bonds and the inorganic additive of the silicones form inorganic
Oxygen barrier heat-insulating protective layer；
S2：Appropriate solvent is provided, the binding agent, organic additive are added into the solvent be mixed into
One colloid；
S3：The progress of the positive electrode active materials, conductive agent and inorganic additive is dry-mixed, and be well mixed；
S4：To adding the solvent as the mixture obtained by step S3, the amount of the solvent is with to soak the table of dry powder
Face is defined；
S5：Colloid made from step S2 is added in the powder mixture of moistened surface made from step S4 and stirred
It is even；
S6：Collector is provided, well mixed cell positive material is coated on the collector, then dried
Dry, roll-in is to form positive plate.
Further, inorganic additive accounts for the 10% of the gross mass of the functional additive in the functional additive
~30%.
Further, stirring condition is that 10 minutes are stirred under 1Hz~1000Hz revolution or/and rotation extremely in step s3
12 hours.
Compared with prior art, the functional additive is added in positive plate, can both reduce and drawn by temperature abruptly increase
The burning risen or the possibility of blast, improve the safety of acupuncture performance of battery, while avoiding additive directly and cathode contact, keep away
Exempt from the capacitance loss brought by additive and negative pole compatibility.In addition, being mixed using organic additive and inorganic additive substep
Use, additive can not only be enable to be well mixed with positive electrode, conductive agent, binding agent, and the two can act synergistically, and enter
One step improves fire resistance, improves the safety of acupuncture performance of battery.
Embodiment
The specific embodiment of the present invention is further elaborated below.It should be appreciated that herein to the present invention
The protection domain that the explanation of embodiment is not intended to limit the present invention.
A kind of cell positive material that the present invention is provided, it includes positive electrode active materials, conductive agent, binding agent, Yi Jigong
Energy property additive, the mass ratio of four kinds of components is 95:2.5:1.5:1.It is understood, however, that preparing the positive pole
Piece, in addition it is also necessary to the component materials such as solvent, collector, due to the content known by its those skilled in the art, the solvent
Can be NMP, its component weight ratio can be adjusted as needed, so no longer as electrode just in the present embodiment
A part for the gross mass of pole material illustrates its mass ratio.The collector can be a finished-product material, for example, can be selected from
Aluminium foil, Punching steel strip etc..In the present embodiment, aluminium foil can be selected as plus plate current-collecting body.By by four kinds of above-mentioned materials
Positive plate can be made by being coated on the collector, and it is prior art, is also no longer described in detail herein.
The positive electrode active materials can be the one or more in cobalt acid lithium, LiMn2O4, LiFePO 4, lithium nickelate.
The conductive agent can be natural flake graphite, micro crystal graphite or conductive carbon black.In the present embodiment, the conductive agent is natural
Crystalline flake graphite, its parts by weight are 2.5.
The functional additive includes inorganic additive and organic additive.The inorganic additive be boric acid, borax,
At least one of molybdenum oxide, zinc oxide, tin oxide and iron oxide or several mixtures, the organic additive are silicon tree
Fat, the silicones can act synergistically to improve fire resistance with the inorganic additive.The binding agent can be poly- inclined fluorine
One or more of mixtures in ethene, polytetrafluoroethylene (PTFE), CMC.In the present embodiment, the binding agent
For polytetrafluoroethylene (PTFE), its parts by weight is 1.5.The functional additive includes inorganic additive and organic additive.The nothing
Machine additive is at least one of boric acid, borax, molybdenum oxide, zinc oxide, tin oxide and iron oxide or several mixtures, institute
It can be that silicon oxygen bond and/or silicon-carbon bonds and cracking carbon-coating silicones can be cracked to form in high temperature to state organic additive.By
When above-mentioned material is preparing positive plate, silicones can move to material surface, and the silicones will be cracked in high temperature
And silicon oxygen bond and/or silicon-carbon bonds and cracking carbon-coating are generated, the silicon oxygen bond and/or silicon-carbon bonds of these generations are formed with inorganic additive
Inorganic oxygen barrier heat-insulating protective layer.Such inorganic oxygen barrier heat-insulating protective layer can both prevent analyte from escaping, and can suppress material again
The thermal decomposition of material improves fire-retardant purpose so as to reach.In addition, the cracking carbon-coating that the silicones is generated can also completely cut off outer
The air and heat on boundary, reduce the combustibility of material.On the other hand, the amino or fluorine that silicones is decomposed can capture combustion reaction
In free radical, so as to prevent flame transmission, decline the flame intensity of combustion zone, make combustion velocity decline until eventually
Only.From the above mentioned, the silicones can be that can improve fire resistance with the synergy of the inorganic additive.The silicon tree
Fat is at least one of methyl silicon resin, methylbenzene silicones, poly- methyl silicon resin, amino silicone, fluorine silicon resin.Enter one
Step ground, the silicones can also be amino silicone or fluorine silicon resin.Inorganic additive accounts for institute in the functional additive
State the 10%~30% of the gross mass of functional additive.It will, of course, be appreciated that, above-mentioned any silicones all may be used
To occur above-mentioned synergy with any one inorganic additive to provide fire resistance.
Got the raw materials ready according to above-mentioned title material and parts by weight, then preparing described use cell positive material just
The preparation method of pole piece, specifically includes the following steps：
S1：Positive electrode active materials, conductive agent, binding agent and functional additive are pressed to the mass ratio of four kinds of components
For 95:2.5:1.5:1 is got the raw materials ready, and the functional additive includes inorganic additive and organic additive；
S2：Appropriate solvent is provided, the binding agent, organic additive are added into the solvent be mixed into
One colloid；
S3：The progress of the positive electrode active materials, conductive agent and inorganic additive is dry-mixed, and be well mixed；
S4：To adding the solvent as the mixture obtained by step S3, the addition of the solvent is to soak dry powder
Surface is defined；
S5：Colloid made from step S2 is added in the powder mixture of moistened surface made from step S4 and stirred
It is even；
S6：Collector is provided, well mixed cell positive material is coated on the collector, then dried
Dry, roll-in is to form positive plate.
In step s 2, the colloid should be a kind of viscous pasty state, it is not possible to which flowing is defined naturally." homogeneous " should be
It is full and uniform, it is impossible to occur conglomeration, the phenomenon such as layering.
In step s3, its stirring condition is that stirring is 10 minutes to 12 small under 1Hz~1000Hz revolution or/and rotation
When.In this step, it is molten due to being added after addition colloid is dry-mixed by the progress of positive electrode active materials, conductive agent and inorganic additive
Agent soaks powder surface, on the one hand positive electrode, conductive agent and inorganic additive can be made to be uniformly dispersed in colloid, another
Aspect can reduce the surface tension of active material, so that the reunion between preventing solid particle, is more beneficial for the uniform of slurry
Mixing, improves the uniformity and processing characteristics of pole piece.
In step S2, S3, S5, those skilled in the art are all it is to be understood that the stirring can be with de-airing mixer
It is middle to carry out.The de-airing mixer can be according to the actual needs to its rotation or/and revolution frequency be adjusted, its stir when
Between be also to set according to actual needs.
Finally, by step S6, the anode sizing agent is coated, dry and roll-in after can form positive plate.Extremely
The technology known by those skilled in the art is should be in the method and apparatus of the coating, drying and roll-in, herein no longer
Repeat.
Above-mentioned positive plate is cut into small pieces, then welds lug can be made anode pole piece, arrange in pairs or groups by negative pole material
Expect the cathode pole piece being made, electrolyte uses LiF6PO4, electrolyte is equipped with for EC/EMC dicyandiamide solutions, and lithium salt is 1M/L,
Lithium ion battery can be made.
Compared with prior art, the functional additive is added in positive plate, can both reduce and drawn by temperature abruptly increase
The burning risen or the possibility of blast, improve the safety of acupuncture performance of battery, while avoiding additive directly and cathode contact, keep away
Exempt from the capacitance loss brought by additive and negative pole compatibility.In addition, being mixed using organic additive and inorganic additive substep
Use, additive can not only be enable to be well mixed with positive electrode, conductive agent, binding agent, and the two can act synergistically, and enter
One step improves fire resistance, improves the safety of acupuncture performance of battery.
Presently preferred embodiments of the present invention is these are only, is not used to limit to protection scope of the present invention, it is any in the present invention
Modification, equivalent substitution or improvement in spirit etc., all cover in scope of the presently claimed invention.
Claims (10)
1. a kind of cell positive material, it is characterised in that：The cell positive material includes positive electrode active materials, conductive agent, viscous
Agent and functional additive are tied, the mass ratio of four kinds of components is 95:2.5:1.5:1, the functional additive includes nothing
Machine additive and organic additive, the inorganic additive is in boric acid, borax, molybdenum oxide, zinc oxide, tin oxide and iron oxide
At least one or several mixture, the organic additive is can be cracked to form silicon oxygen bond and/or silicon in high temperature
The silicones of carbon key and cracking carbon-coating, the silicones can decomposite amino or fluorine, the silicon oxygen bond of the silicones in cracking
And/or silicon-carbon bonds form inorganic oxygen barrier heat-insulating protective layer to improve fire resistance with inorganic additive.
2. cell positive material as claimed in claim 1, it is characterised in that：The positive electrode active materials are cobalt acid lithium, mangaic acid
One or more in lithium, LiFePO 4, lithium nickelate.
3. cell positive material as claimed in claim 1, it is characterised in that：The conductive agent is natural flake graphite, crystallite
Graphite or conductive carbon black.
4. cell positive material as claimed in claim 1, it is characterised in that：The binding agent is Kynoar, polytetrafluoro
One or more of mixtures in ethene, CMC.
5. cell positive material as claimed in claim 1, it is characterised in that：The silicones is methyl silicon resin, methylbenzene
At least one of silicones, poly- methyl silicon resin, amino silicone, fluorine silicon resin.
6. cell positive material as claimed in claim 1, it is characterised in that：The silicones is amino silicone or fluorine silicon tree
Fat.
7. cell positive material as claimed in claim 1, it is characterised in that：Inorganic additive is accounted in the functional additive
The 10%~30% of the gross mass of the functional additive.
8. a kind of preparation method of the positive plate of use cell positive material：It is characterized in that comprising the following steps：
S1：The mass ratio that positive electrode active materials, conductive agent, binding agent and functional additive are pressed into four kinds of components is 95:
2.5:1.5:1 is got the raw materials ready, and the functional additive includes inorganic additive and organic additive, and the inorganic additive is
At least one of boric acid, borax, molybdenum oxide, zinc oxide, tin oxide and iron oxide or several mixtures, organic addition
Agent is that the silicones of silicon oxygen bond and/or silicon-carbon bonds and cracking carbon-coating can be cracked to form in high temperature, and the silicones is splitting
Xie Shineng decomposites amino or fluorine, and it is exhausted that silicon oxygen bond and/or silicon-carbon bonds and the inorganic additive of the silicones form inorganic oxygen barrier
Thermal-protective coating；
S2：Appropriate solvent is provided, by the binding agent, organic additive be added to the solvent be mixed into it is homogeneous
Colloid；
S3：The progress of the positive electrode active materials, conductive agent and inorganic additive is dry-mixed, and be well mixed；
S4：The solvent is added to as the mixture obtained by step S3, the amount of the solvent is defined by the surface for soaking dry powder；
S5：Colloid made from step S2 is added in the powder mixture of moistened surface made from step S4 and stirred；
S6：Collector is provided, well mixed cell positive material is coated on the collector, is then dried, roller
Press to form positive plate.
9. the preparation method of cell negative electrode material as claimed in claim 8, it is characterised in that：Nothing in the functional additive
Machine additive accounts for the 10%~30% of the gross mass of the functional additive.
10. the preparation method of the negative plate of cell negative electrode material is used as claimed in claim 8, it is characterised in that：In step
Stirring condition is to be stirred 10 minutes to 12 hours under 1Hz~1000Hz revolution or/and rotation in S3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710090297.9A CN107170987A (en) | 2017-02-20 | 2017-02-20 | A kind of preparation method of the positive plate of cell positive material and the use cell positive material |
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| CN201710090297.9A CN107170987A (en) | 2017-02-20 | 2017-02-20 | A kind of preparation method of the positive plate of cell positive material and the use cell positive material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110943218A (en) * | 2019-10-30 | 2020-03-31 | 天津力神电池股份有限公司 | Positive electrode slurry, preparation method thereof, positive plate and lithium iron phosphate battery |
| CN111725511A (en) * | 2020-06-29 | 2020-09-29 | 东莞市魔方新能源科技有限公司 | A lithium ion secondary battery pole piece and lithium ion secondary battery |
| CN112018397A (en) * | 2020-09-21 | 2020-12-01 | 珠海冠宇电池股份有限公司 | Positive plate and battery |
| CN114583247A (en) * | 2022-02-28 | 2022-06-03 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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Application publication date: 20170915 |