CN104269558A - Carbon material-filled binding agent for lithium battery and preparation method of carbon material-filled binding agent - Google Patents
Carbon material-filled binding agent for lithium battery and preparation method of carbon material-filled binding agent Download PDFInfo
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- CN104269558A CN104269558A CN201410519423.4A CN201410519423A CN104269558A CN 104269558 A CN104269558 A CN 104269558A CN 201410519423 A CN201410519423 A CN 201410519423A CN 104269558 A CN104269558 A CN 104269558A
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- binding agent
- carbon element
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon material-filled binding agent for a lithium battery. The carbon material-filled binding agent is compounded from polyvinylidene fluoride (PVDF) and a carbon material, wherein the carbon material is one or a mixture of conductive black (SP), carbon fiber (VGCF) and a carbon nano tube (CNT). According to the carbon material-filled binding agent, the carbon material is added in the polyvinylidene fluoride (PVDF), thus the transmission rate of electrons is increased, the conductivity is enhanced, the battery polarization is reduced, and the low-temperature property of the battery is improved.
Description
Technical field
The present invention relates to and relate to a kind of field of lithium, particularly relate to bonder for lithium ion batteries of a kind of material with carbon element filling and preparation method thereof.
Background technology
Lithium battery is also known as rocking chair batteries, and because its energy density is high, long service life, the feature such as environment friendly and pollution-free, as the representative of 21 century green energy resource, has been widely used in the various aspects of people's daily life.In recent years, the electrical source of power of electric automobile and the accumulation power supply of energy-storage system is more applied to.Lithium battery is primarily of positive pole, and negative pole, barrier film, electrolyte, the compositions such as binding agent, wherein binding agent has become an individual branches in lithium electricity industrial chain.Binding agent conventional at present divides two kinds, and one is aqueous binders, with butadiene-styrene rubber (SBR) for representative; One is oiliness binding agent, with Kynoar (PVDF) for representative.Though two kinds of binding agents proportion in the component of lithium electricity is few, have indispensable effect, but binding agent is all insulators, is added in lithium electricity component, will certainly battery polarization be increased, affect the cryogenic property of battery.The material of conduction if can be able to induce one in the macromolecular chain of binding agent, to reduction polarization, improves cryogenic property helpful.The present invention's binding agent used is oiliness binding agent Kynoar (PVDF).
Separately have China Patent No. to be: 201010285914.9, date of publication is 2011.2.23, discloses a kind of lithium ion battery anode glue size preparation method, aims to provide a kind of processing technology of anode slurry of lithium iron phosphate battery.This preparation method mainly adopts high temperature drying to dissolve, first pre-dispersed, adds in agitator by solvent and bonding agent, be filled with dry gas use mechanical agitation, then fill dry gas protection put into hot environment leave standstill, by bonding agent high-temperature digestion; Conductive agent and active material adopt dry powder ball milling hybrid mode, are added by conductive agent by ceramic ball action in active material, are evenly dispersed in by conductive agent in active material; The active material mixed is added in adhesive solution, is filled with dry gas and uses mechanical agitation mode active material and bonding agent to be uniformly dispersed, be prepared into anode sizing agent.Its feature is each component of anode sizing agent to be fully uniformly mixed, but the flow process of this technique is loaded down with trivial details, complicated process of preparation, different processing steps needs to change different equipment, which adds slurry aerial open-assembly time, probably cause excessive moisture to enter slurry, be unfavorable for the dispersion of slurry; And the method binding agent used remains traditional insulating properties binding agent, non-conductive, battery is unfavorable for the transmission of electronics in charge and discharge process, and then the electrical property that can affect battery plays.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the invention provides adhesive for lithium battery of a kind of material with carbon element filling and preparation method thereof, the binding agent prepared by the method is compared to traditional binding agent, by adding material with carbon element, both improve the transmission rate of electronics, enhance conductivity, reduce battery polarization, improve the cryogenic property of battery.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
The adhesive for lithium battery that material with carbon element is filled, is characterized in that: described binding agent is composited by Kynoar (PVDF) and material with carbon element.
Described material with carbon element is the mixture of one or more in conductive black (SP), carbon fiber (VGCF), carbon nano-tube (CNT).
The mass ratio of described material with carbon element and Kynoar PVDF is 1:6-9.
A preparation method for the adhesive for lithium battery that material with carbon element is filled, comprises the steps:
(1) by Kynoar (PVDF) and material with carbon element powder evenly blended at 200 DEG C, become thick liquid;
(2) cool under thick liquid being placed room temperature;
(3) solid cooled is placed in ball mill ball milling powdered;
(4) gained powder is placed in 60 DEG C of baking ovens again drying obtain adhesive powder.
The present invention has the following advantages:
1, the bonder for lithium ion batteries of a kind of material with carbon element filling of the present invention, be composited by Kynoar (PVDF) and material with carbon element, by adding material with carbon element at Kynoar (PVDF), both improve the transmission rate of electronics, enhance conductivity, reduce battery polarization, improve the cryogenic property of battery.
2, the material with carbon element in the present invention is the mixture of one or more in conductive black (SP), carbon fiber (VGCF), carbon nano-tube (CNT).Above-mentioned material with carbon element, raw material is easy to get, low price, is material very common on current lithium electricity market.Wherein, conductive black (SP) is point-like grain structure, carbon fiber (VGCF) is chain structure, carbon nano-tube (CNT) is that surface has very multi-functional chain structure, their each own respective design features, corresponding design feature has again respective advantage, and such as point-like grain structure particle is little, easy dispersion, is convenient to slurry processing; Chain structure particle is large, not easily disperses, but excellent electric conductivity.Several material with carbon element is mixed, respective advantage can be combined, learn from other's strong points to offset one's weaknesses.
3, the weight ratio of material with carbon element of the present invention and Kynoar PVDF is 1:6-9.By the caking property that this proportioning is to ensure based on binding agent, the conductivity of binding agent is auxiliary, if conducting polymer too high levels, can reduce the caking property of binding agent, be unfavorable for the processing of battery.
4, the preparation method of binding agent of the present invention, technological process is simple, and raw material is easy to get, and processing cost is low, and test effect is good.
Embodiment
Embodiment 1
(1) by conductive black powder (SP) and Kynoar (PVDF) evenly blended at 200 DEG C by the mass ratio of 1:9, become thick liquid;
(2) cool under obtained thick liquid being placed room temperature, obtain cooling solid;
(3) solid cooled is placed in ball mill ball milling powdered;
(4) gained powder is placed in 60 DEG C of baking ovens again drying obtain adhesive powder SP-PVDF.
Gained binding agent is used for battery make and test, battery used is:
Positive pole: active material is synthetic electrode material, binding agent SP-PVDF 4%, the 16um thickness aluminum foil current collector of content 91%, conductive carbon black content 5%, synthesis, pole piece thickness 135um after colding pressing.
Negative pole: binding agent SP-PVDF 4%, the 15um thickness copper foil current collector of active material content of graphite 93%, conductive carbon black content 3%, synthesis, pole piece thickness 98um after colding pressing.
Barrier film PE single-layer septum, battery design capacity 5Ah.
Detection method:
Detect the charge-discharge characteristic of battery with Arbin BT2000 tester, idiographic flow is:
1, under normal temperature with 1C electric current by first for battery constant current again constant voltage charge to 3.8V, charge by electric current be 0.01A;
2, under normal temperature static 5 minutes, with 1C electric current by battery constant-current discharge to 2.0V, read the 1C discharge capacity of battery.
With the AC internal Resistance putting internal resistance test device detection battery day
Embodiment 2
(1) by carbon fiber powder (VGCF) and Kynoar (PVDF) evenly blended at 200 DEG C by the mass ratio of 1:6, become thick liquid;
(2) cool under obtained thick liquid being placed room temperature;
(3) solid cooled is placed in ball mill ball milling powdered;
(4) gained powder is placed in 60 DEG C of baking ovens again drying obtain adhesive powder VGCF-PVDF.
Gained binding agent is used for battery make and test, battery making and detection method are with embodiment 1.
Embodiment 3
(1) by carbon nanotube powder (CNT) and Kynoar (PVDF) evenly blended at 200 DEG C by the mass ratio of 1:8, become thick liquid;
(2) cool under obtained thick liquid being placed room temperature;
(3) solid cooled is placed in ball mill ball milling powdered;
(4) gained powder is placed in 60 DEG C of baking ovens again drying obtain adhesive powder CNT-PVDF.
Gained binding agent is used for battery make and test, battery making and detection method are with embodiment 1.
Embodiment 4
(1) conductive black (SP) is mixed by the mass ratio of 1:1 with carbon fiber (VGCF), by gained mixture SP-VGCF and Kynoar (PVDF) evenly blended at 200 DEG C by the mass ratio of 1:9, become thick liquid;
(2) cool under obtained thick liquid being placed room temperature;
(3) solid cooled is placed in ball mill ball milling powdered;
(4) gained powder is placed in 60 DEG C of baking ovens again drying obtain adhesive powder SP-VGCF-PVDF.
Gained binding agent is used for battery make and test, battery making and detection method are with embodiment 1.
Embodiment 5
(1) conductive black (SP) is mixed by the mass ratio of 1:1 with carbon nano-tube (CNT), by gained mixture SP-CNT and Kynoar (PVDF) evenly blended at 200 DEG C by the mass ratio of 1:8, become thick liquid;
(2) cool under obtained thick liquid being placed room temperature;
(3) solid cooled is placed in ball mill ball milling powdered;
(4) gained powder is placed in 60 DEG C of baking ovens again drying obtain adhesive powder SP-CNT-PVDF.
Gained binding agent is used for battery make and test, battery making and detection method are with embodiment 1.
Embodiment 6
(1) carbon nano-tube (CNT) is mixed by the mass ratio of 1:1 with carbon fiber (VGCF), by gained mixture C NT-VGCF and Kynoar (PVDF) evenly blended at 200 DEG C by the mass ratio of 1:9, become thick liquid;
(2) cool under obtained thick liquid being placed room temperature;
(3) solid cooled is placed in ball mill ball milling powdered;
(4) gained powder is placed in 60 DEG C of baking ovens again drying obtain adhesive powder CNT-VGCF-PVDF.
Gained binding agent is used for battery make and test, battery making and detection method are with embodiment 1.
Comparative example
Adopt undressed PVDF powder to make battery, concrete manufacture method is as follows:
Positive pole: active material is synthetic electrode material, content 91%, conductive carbon black content 5%, undressed PVDF 4%, 16um thickness aluminum foil current collector, pole piece thickness 138um after colding pressing.
Negative pole: active material content of graphite 93%, conductive carbon black content 3%, undressed PVDF 4%, 15um thickness copper foil current collector, pole piece thickness 100um after colding pressing.
Barrier film is PP/PE/PP tri-layers of barrier film, battery design capacity 5Ah.
Battery detection method is with embodiment 1.
Table 1 embodiment and comparative example make the discharge capacity at 25 DEG C of battery
The AC internal Resistance of battery made by table 2 embodiment and comparative example
Negative 20 DEG C of cryogenic properties of battery made by table 3 embodiment and comparative example
From test result, the binding agent of filling material with carbon element is less than unfilled AC internal Resistance, and 25 DEG C of discharge capacities are high, and negative 20 DEG C of cryogenic properties have a clear superiority in.
Claims (4)
1. an adhesive for lithium battery for material with carbon element filling, is characterized in that: described binding agent is composited by Kynoar (PVDF) and material with carbon element.
2. the adhesive for lithium battery of material with carbon element filling according to claim 1, is characterized in that: described material with carbon element is the mixture of one or more in conductive black (SP), carbon fiber (VGCF), carbon nano-tube (CNT).
3. the adhesive for lithium battery of material with carbon element filling according to claim 1, is characterized in that: the mass ratio of described material with carbon element and Kynoar PVDF is 1:6-9.
4. the preparation method of the adhesive for lithium battery of material with carbon element filling according to claim 1, comprises the steps:
(1) by Kynoar (PVDF) and material with carbon element powder evenly blended at 200 DEG C;
(2) cool under thick liquid being placed room temperature;
(3) solid cooled is placed in ball mill ball milling powdered;
(4) gained powder is placed in 60 DEG C of baking ovens again drying obtain adhesive powder.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410519423.4A CN104269558A (en) | 2014-09-30 | 2014-09-30 | Carbon material-filled binding agent for lithium battery and preparation method of carbon material-filled binding agent |
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| CN201410519423.4A CN104269558A (en) | 2014-09-30 | 2014-09-30 | Carbon material-filled binding agent for lithium battery and preparation method of carbon material-filled binding agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020058626A1 (en) * | 2018-09-21 | 2020-03-26 | Arkema France | Compositions for bipolar plates and processes for manufacturing said compositions |
| CN113793938A (en) * | 2021-08-27 | 2021-12-14 | 成都锂能科技有限公司 | PVDF binder for lithium battery/sodium battery/potassium battery positive electrode and preparation method thereof |
| CN114758814A (en) * | 2022-03-28 | 2022-07-15 | 诺瑞(深圳)新技术有限公司 | Conductive composite material and preparation method and application thereof |
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| JPH10255844A (en) * | 1997-03-10 | 1998-09-25 | Sony Corp | Nonaqueous electrolyte secondary battery |
| CN1253953C (en) * | 2003-02-19 | 2006-04-26 | 松下电器产业株式会社 | Electrode for a battery and production method thereof |
| CN102906911A (en) * | 2010-03-23 | 2013-01-30 | 阿克马法国公司 | Masterbatch of carbon-based conductive fillers for liquid formulations, especially in li-ion batteries |
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2014
- 2014-09-30 CN CN201410519423.4A patent/CN104269558A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH10255844A (en) * | 1997-03-10 | 1998-09-25 | Sony Corp | Nonaqueous electrolyte secondary battery |
| CN1253953C (en) * | 2003-02-19 | 2006-04-26 | 松下电器产业株式会社 | Electrode for a battery and production method thereof |
| CN102906911A (en) * | 2010-03-23 | 2013-01-30 | 阿克马法国公司 | Masterbatch of carbon-based conductive fillers for liquid formulations, especially in li-ion batteries |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020058626A1 (en) * | 2018-09-21 | 2020-03-26 | Arkema France | Compositions for bipolar plates and processes for manufacturing said compositions |
| FR3086291A1 (en) * | 2018-09-21 | 2020-03-27 | Arkema France | COMPOSITIONS FOR BIPOLAR PLATES AND METHODS OF MAKING SAME |
| CN112654663A (en) * | 2018-09-21 | 2021-04-13 | 阿科玛法国公司 | Composition for bipolar plates and method for manufacturing said composition |
| JP2022501465A (en) * | 2018-09-21 | 2022-01-06 | アルケマ フランス | Compositions for bipolar plates and methods for producing said compositions |
| CN112654663B (en) * | 2018-09-21 | 2024-01-30 | 阿科玛法国公司 | Composition for bipolar plate and method for manufacturing the same |
| JP7426993B2 (en) | 2018-09-21 | 2024-02-02 | アルケマ フランス | Compositions for bipolar plates and methods for producing said compositions |
| US12087976B2 (en) | 2018-09-21 | 2024-09-10 | Arkema France | Compositions for bipolar plates and processes for manufacturing said compositions |
| CN113793938A (en) * | 2021-08-27 | 2021-12-14 | 成都锂能科技有限公司 | PVDF binder for lithium battery/sodium battery/potassium battery positive electrode and preparation method thereof |
| CN114758814A (en) * | 2022-03-28 | 2022-07-15 | 诺瑞(深圳)新技术有限公司 | Conductive composite material and preparation method and application thereof |
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