CN102244264B - Graphine composite electric conduction agent for iron phosphate lithium battery and preparation method thereof - Google Patents
Graphine composite electric conduction agent for iron phosphate lithium battery and preparation method thereof Download PDFInfo
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- CN102244264B CN102244264B CN2011101297558A CN201110129755A CN102244264B CN 102244264 B CN102244264 B CN 102244264B CN 2011101297558 A CN2011101297558 A CN 2011101297558A CN 201110129755 A CN201110129755 A CN 201110129755A CN 102244264 B CN102244264 B CN 102244264B
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a graphine composite electric conduction agent for an iron phosphate lithium battery, and simultaneously discloses a preparation method of the electric conduction agent. The electric conduction agent provided by the invention consists of graphine, active carbon and a bonding agent in a weight ratio of 1:(0.001-0.1):(0.01-1). The preparation method comprises the following steps: 1) preparing a solution A; 2) preparing a solution B; and 3) preparing the electric conduction agent. According to the invention, the preparation method is simple, the prepared electric conduction agent has the advantages of uniform dispersion, good stability, high electron conduction capability and uniform heat conduction, and the electric conduction agent has higher liquid absorption and liquid protection capabilities when being doped into the iron phosphate lithium battery; and the electric chemical property of the iron phosphate lithium battery which is prepared by adopting the electric conduction agent provided by the invention is improved prominently, compared with the iron phosphate lithium anode material in which the composite electric conduction agent is not doped, when the prepared graphite composite electric conduction agent is doped into the 50AH iron phosphate lithium anode material, the alternating current internal resistance is reduced by 20%, and the circulating service life is improved by 15%.
Description
Technical field
The present invention relates to technical field of lithium ion secondary, be specifically related to a kind of conductive agent used for lithium iron phosphate battery and preparation method thereof.
Background technology
Lithium rechargeable battery is as a kind of novel high-energy secondary power supply, has that specific energy is large, discharging voltage balance, voltage high and low temperature performance is good, pollution-free, security performance is superior and storage and long working life, utilance advantages of higher.The above-mentioned advantage of lithium rechargeable battery impels the various countries scientist competitively to study, thereby has promoted the fast development of lithium rechargeable battery.The positive electrode of lithium rechargeable battery has a variety of, mainly contains cobalt acid lithium, lithium nickelate, the LiMn2O4 of spinelle shape and the LiFePO4 of olivine shape thereof etc. of stratiform.And ferric phosphate lithium cell is a kind of heavy-duty battery that just occurred in recent years, and causes people's extensive attention in the advantage aspect environmental protection, security performance and cycle life.The cycle life of ferric phosphate lithium cell reaches 2000 times, and single battery overcharged voltage 30V does not burn, and puncture is not exploded, and has the advantages such as nontoxic, pollution-free, that security performance is good, raw material wide material sources, low price, and the life-span is long.
The electrode reaction of lithium rechargeable battery comprises the transmission of electronics and the transmission of ion, so just requires electrode that good conductivity will be arranged, and guarantees the unimpeded of electron propagation ducts; Also some pore structures to be arranged simultaneously, can hold electrolyte, guarantee the smooth of ion transfer.The requirement that only reaches this two aspect can guarantee that electrode active material has higher utilance and good cyclical stability.The positive pole of ferric phosphate lithium cell adopts LiFePO4 as active material, but therefore the poorly conductive of LiFePO4 itself often adopts to add conductive agent to improve its conductivity in active material when forming electrode.The conductive agent that at present ferric phosphate lithium cell is commonly used comprises the graininess conductive agent, as the compound of: acetylene black, Super P, granular graphite, metal dust and two kinds or two or more variable grain shape conductive materials etc.; Fibrous conductive agent, as: (the patent No.s: CN200810144527.6) such as gas-phase growth of carbon fibre, carbon nano-tube and metallic fiber, although above conductive agent can improve the contact probability with the active material LiFePO4, reduce internal resistance, reduce polarization, and then improve the cyclical stability of electrode, finally form effective conductive network and fixed electrode material in electrode, but its increase rate is limited.
Graphene is a kind of new material that rises rapidly in recent years.Its structure can be understood as the graphite of individual layer, therefore has extremely good conductivity, and wherein the movement velocity of electronics has reached 1/300 of the light velocity.The two-dimensional nano layer structure of while Graphene uniqueness and huge specific area have more outstanding advantage when material modified as interpolation than carbon nano-tube or carbon black etc.And active carbon is owing to having than carbon nano-tube or the larger specific area of Graphene, and its specific area is up to 2000m
2/ g is than 200 m of carbon nano-tube
2/ g has raising by a relatively large margin, its huge specific area can improve the imbibition liquid-keeping property of material, and compound with the strong Graphene of its conductivity, the advantage that both can bring into play the high electron conduction of Graphene improves the transmission rate of ion, can bring into play again imbibition liquid-keeping property and the transmittability of lithium ion and then the stability of raising monomer whose battery that the huge specific area advantage of active carbon improves active material in course of reaction.
Summary of the invention
For the conduction problem that lithium rechargeable battery in above ferric phosphate lithium cell exists, the object of the present invention is to provide the strong and imbibition of a kind of electronic conduction ability protect liquid strong conductive agent used for lithium iron phosphate battery and preparation method thereof.
For realizing above purpose, the technical solution adopted in the present invention is: a kind of conductive agent used for lithium iron phosphate battery, be comprised of Graphene, active carbon and binding agent, the weight ratio of Graphene, active carbon and binding agent is: 1:(0.001～0.1): (0.01～1).
Described binding agent is polypropylene cyanogen and/or polyacrylic acid, when binding agent is polypropylene cyanogen and polyacrylic composition, polypropylene cyanogen and polyacrylic weight ratio are: polypropylene cyanogen: polyacrylic acid is 0.5～5:1, and wherein, polyacrylic molecular weight is 3000 ~ 5000; The molecular weight of polypropylene cyanogen is 2000 ~ 5000.
A kind of preparation method of conductive agent used for lithium iron phosphate battery by weight percentage, comprises the following steps: 1) preparation A solution, 2) preparation B solution, 3) preparation conductive agent; It is characterized in that:
1) preparation A solution: get 1 part of Graphene, 0.01～1 part of binding agent, Graphene and binding agent are put into the ultrasonic dispersion of redistilled water, the time is 5 minutes, and supersonic frequency is that 20 ~ 60KHZ obtains A solution.
The consumption of described redistilled water is: 20～200.
The specific area of described active carbon is 1000 ~ 2000m
2/ g.
2) preparation B solution: get 0.01～1 part of active carbon 0.001～0.1 and binding agent put into ultrasonicly in redistilled water be separated into for 5 ~ 15 times, supersonic frequency is that 20KHZ obtains B solution.
3) preparation conductive agent: (ultrasonic time is 5 ~ 15 minutes) slowly splashes into B solution in A solution under hyperacoustic condition, make the weight ratio of Graphene, active carbon and binding agent be: 1:(0.001～0.1): (0.01～1) namely makes conductive agent used for lithium iron phosphate battery.
The present invention, the preparation method is simple, and the conductive agent that makes is uniformly dispersed, good stability.The electronic conduction ability of conductive agent is strong and the heat conduction is even, has stronger imbibition liquid-keeping property inside being doped to ferric phosphate lithium cell, chemical property is significantly improved, the Graphene combined conductive agent of its preparation is doped to inside the 50AH lithium iron phosphate positive material, more its AC internal Resistance of the lithium iron phosphate positive material of doped and compounded conductive agent does not reduce by 20%, and cycle life improves 15%.
Embodiment
Embodiment 1:
The conductive agent used for lithium iron phosphate battery of the present embodiment is comprised of Graphene, active carbon and polypropylene cyanogen, and the weight ratio of Graphene, active carbon and polypropylene cyanogen is: Graphene: active carbon: polypropylene cyanogen=1:0.1:1.
The preparation method of the present embodiment conductive agent used for lithium iron phosphate battery, concrete steps are as follows:
Take out, the complete heat of preliminary treatment distributes, and finally the unfavorable shadow of battery generation is taken 1g Graphene and 0.5g polypropylene cyanogen, and the molecular weight of polypropylene cyanogen is 2000 ~ 5000; Put into afterwards the 50ml redistilled water, and ultrasonic dispersion 5 minutes (being designated as A solution) under hyperacoustic condition; Take simultaneously 0.1g active carbon and 0.5g polypropylene cyanogen thereof, the specific area of active carbon is 1500m
2/ g, and will put in the 50ml redistilled water, ultrasonic dispersion 5 minutes, supersonic frequency is 20KHZ, obtain B solution, B solution is slowly joined in A solution, and continue ultrasonic dispersion 15 minutes, supersonic frequency is 30KHZ, makes at last conductive agent used for lithium iron phosphate battery.
Embodiment 2:
The present embodiment conductive agent used for lithium iron phosphate battery is comprised of Graphene, active carbon and polyacrylic acid, and Graphene, active carbon and polyacrylic weight ratio are: 1:0.1:1.
The preparation method of the present embodiment conductive agent used for lithium iron phosphate battery, concrete steps are as follows:
Take 1g Graphene and 0.1g polyacrylic acid thereof, put into afterwards the 100ml redistilled water, and ultrasonic dispersion 15 minutes (A solution) under hyperacoustic condition; Take simultaneously 0.1g active carbon and 0.9g polyacrylic acid thereof, the specific area of active carbon is 1000m
2/ g, and will put in the 50ml redistilled water, ultrasonic dispersion 15 minutes, supersonic frequency is 40KHZ, obtain B solution, B solution is slowly joined in A solution, and continue ultrasonic dispersion 15 minutes, supersonic frequency is 20KHZ, makes at last conductive agent used for lithium iron phosphate battery.
Embodiment 3
The present embodiment conductive agent used for lithium iron phosphate battery is comprised of Graphene, active carbon and polypropylene cyanogen, and the weight ratio of Graphene, active carbon and polypropylene cyanogen is: Graphene: active carbon: polypropylene cyanogen=1:0.1:1.
The preparation method of the present embodiment conductive agent used for lithium iron phosphate battery, concrete steps are as follows:
Take 1g Graphene and 0.1g polypropylene cyanogen thereof, put into afterwards the 150ml redistilled water, and ultrasonic dispersion 5 minutes (A solution) under hyperacoustic condition; Take simultaneously 0.1g active carbon and 0.9g polypropylene cyanogen thereof, the specific area of active carbon is 2000m
2/ g also will put in the 50ml redistilled water, ultrasonic dispersion 5 minutes, supersonic frequency is 40KHZ, obtain B solution, B solution is slowly joined in A solution, and continuing ultrasonic dispersion 5 minutes, supersonic frequency is 60KHZ, makes at last conductive agent used for lithium iron phosphate battery.
Embodiment 4
The present embodiment conductive agent used for lithium iron phosphate battery is comprised of Graphene, active carbon and polypropylene cyanogen, and the weight ratio of Graphene, active carbon and polypropylene cyanogen is: Graphene: active carbon: polypropylene cyanogen=1:0.001:1.
The preparation method of the present embodiment conductive agent used for lithium iron phosphate battery, concrete steps are as follows:
Take 1g Graphene and 0.5g polypropylene cyanogen thereof, put into afterwards the 200ml redistilled water, and ultrasonic dispersion 5 minutes (A solution) under hyperacoustic condition; Take simultaneously 0.001g active carbon and 0.5g polypropylene cyanogen thereof, the specific area of active carbon is 12000m
2/ g also will put in the 50ml redistilled water, ultrasonic dispersion 10 minutes, supersonic frequency is 20KHZ, obtain B solution, B solution is slowly joined in A solution, and continuing ultrasonic dispersion 15 minutes, supersonic frequency is 20KHZ, makes at last conductive agent used for lithium iron phosphate battery.
Embodiment 5
The present embodiment conductive agent used for lithium iron phosphate battery, be comprised of Graphene, active carbon, polypropylene cyanogen and polyacrylic acid, Graphene, active carbon, polypropylene cyanogen and polyacrylic weight ratio are: Graphene: active carbon: (polypropylene cyanogen+polyacrylic acid)=1:0.1:0.01.
The preparation method of the present embodiment conductive agent used for lithium iron phosphate battery, concrete steps are as follows:
Take 1g Graphene and 0.005g(polypropylene cyanogen+polyacrylic acid thereof), put into afterwards the 50ml redistilled water, and ultrasonic dispersion 5 minutes (A solution) under hyperacoustic condition; Take simultaneously 0.1g active carbon and 0.005g(polypropylene cyanogen+polyacrylic acid thereof), the specific area of active carbon is 1500m
2/ g also will put in the 50ml redistilled water, ultrasonic dispersion 5 minutes, supersonic frequency is 40KHZ, obtain B solution, B solution is slowly joined in A solution, and continuing ultrasonic dispersion 15 minutes, supersonic frequency is 40KHZ, makes at last conductive agent used for lithium iron phosphate battery.
In conductive agent used for lithium iron phosphate battery provided by the invention, Graphene is compared with active carbon has stronger electric transmission speed and stronger heat dispersion, therefore further composite graphite alkene/binding agent on the basis of active carbon/binding agent composite material, not only can reduce the internal resistance of active carbon/binding agent composite material, can also improve the heat dispersion of cell simultaneously.The active carbon that has simultaneously larger imbibition liquid-keeping property can provide more ion channel again, makes it reach the effect of Graphene and active carbon mutual supplement with each other's advantages, improves the physical and chemical performance of active material, and the consistency of battery is played an important role; Add binding agent not only can reduce the subsidence velocity of conductive agent in conductive agent used for lithium iron phosphate battery provided by the invention, also can improve the dispersion effect of conductive agent, can also improve simultaneously the compatibility of Graphene and active material, in addition, adding of binding agent played important function to the stability that improves conductive agent and the technology stability that closes afterwards the slurry process, can also simplify the slurry process of closing.
Conductive agent used for lithium iron phosphate battery provided by the invention brought into play effectively that graphene conductive is strong, thermal diffusivity is good advantage, can utilize again the strong advantage of its active carbon imbibition liquid-keeping property, and make it produce cooperative effect, significantly improved the chemical property of battery; Simultaneously, binding agent add the decrease speed that not only can reduce conductive agent, improve the shelf-stability of the conductive agent that makes, but also can improve the compatibility of closing Graphene, active carbon and lithium-iron phosphate active material in the slurry process.
Claims (1)
1. the preparation method of the Graphene combined conductive agent used of a ferric phosphate lithium cell, the Graphene combined conductive agent is comprised of Graphene, active carbon and polypropylene cyanogen, its ratio is 1:0.1:1, represented by percentage by weight, the preparation method comprises the following steps: 1) preparation A solution, 2) preparation B solution, 3) preparation conductive agent; It is characterized in that:
1), preparation A solution: take 1g Graphene and 0.5g polypropylene cyanogen, the molecular weight of polypropylene cyanogen is 2000 ~ 5000; Put into the 50ml redistilled water, and ultrasonic dispersion 5 minutes under hyperacoustic condition, A solution obtained;
2), preparation B solution: take 0.1g active carbon and 0.5g polypropylene cyanogen thereof, the specific area of active carbon is 1500m
2/ g, and will put in the 50ml redistilled water, ultrasonic dispersion 5 minutes, supersonic frequency is 20KHZ, obtains B solution;
3), preparation conductive agent: B solution is slowly joined in A solution, and continue ultrasonic dispersion 15 minutes, supersonic frequency is 30KHZ, makes at last conductive agent used for lithium iron phosphate battery.
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| US9249524B2 (en) | 2011-08-31 | 2016-02-02 | Semiconductor Energy Laboratory Co., Ltd. | Manufacturing method of composite oxide and manufacturing method of power storage device |
| CN102509642A (en) * | 2011-11-21 | 2012-06-20 | 余泉茂 | Method for preparing supercapacitor with expanded graphite, grapheme and activated carbon |
| JP6016597B2 (en) | 2011-12-16 | 2016-10-26 | 株式会社半導体エネルギー研究所 | Method for producing positive electrode for lithium ion secondary battery |
| CN102790220B (en) * | 2012-08-27 | 2014-09-10 | 优科能源(漳州)有限公司 | Manufacturing method of diamond-shaped conductive additive for improving liquid absorbing performance of pole piece of lithium ion battery |
| CN102945945A (en) * | 2012-11-16 | 2013-02-27 | 双登集团股份有限公司 | Production method for pole piece of lithium ion battery |
| CN103887514B (en) * | 2014-04-15 | 2016-03-02 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of lithium ion battery anode glue size |
| CN104505515B (en) * | 2014-12-26 | 2016-11-30 | 广东东莞市天润电子材料有限公司 | A kind of ferrous phosphate lithium battery nano-graphite conductive agent and preparation method thereof |
| CN104795569B (en) * | 2015-03-18 | 2017-03-15 | 江苏乐能电池股份有限公司 | Ferric phosphate lithium cell conducting polymer combined conductive agent and preparation method thereof |
| CN105932287B (en) * | 2016-05-24 | 2019-01-22 | 宁波墨西科技有限公司 | A kind of graphene composite conductive agent and preparation method thereof |
| CN106450330B (en) * | 2016-10-21 | 2018-01-30 | 成都新柯力化工科技有限公司 | A kind of special isomery graphene conductive agent of lithium battery and preparation method thereof |
| CN107316751B (en) * | 2017-08-17 | 2019-01-01 | 大英聚能科技发展有限公司 | A kind of dedicated combined conductive agent of super capacitance cell and preparation method thereof |
| CN107808961A (en) * | 2017-10-12 | 2018-03-16 | 南京旭羽睿材料科技有限公司 | A kind of graphene conductive agent |
| CN109841834B (en) * | 2017-11-28 | 2021-06-29 | 横店集团东磁股份有限公司 | Composite conductive agent, preparation method thereof and application of composite conductive agent in positive electrode slurry |
| CN108767245B (en) * | 2018-06-26 | 2021-07-02 | 陕西海恩新材料有限责任公司 | Mixed type anode material and manufacturing method thereof |
| CN111916731A (en) * | 2020-07-27 | 2020-11-10 | 珠海冠宇电池股份有限公司 | Positive plate, preparation method thereof and lithium ion secondary battery comprising positive plate |
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| US8936874B2 (en) * | 2008-06-04 | 2015-01-20 | Nanotek Instruments, Inc. | Conductive nanocomposite-based electrodes for lithium batteries |
| CN101710619A (en) * | 2009-12-14 | 2010-05-19 | 重庆大学 | Electrode plate for lithium ion battery and manufacturing method thereof |
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