CN103000866A - Negative pole material of lithium ion battery and manufacturing method of negative pole of battery - Google Patents
Negative pole material of lithium ion battery and manufacturing method of negative pole of battery Download PDFInfo
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- CN103000866A CN103000866A CN2012105135330A CN201210513533A CN103000866A CN 103000866 A CN103000866 A CN 103000866A CN 2012105135330 A CN2012105135330 A CN 2012105135330A CN 201210513533 A CN201210513533 A CN 201210513533A CN 103000866 A CN103000866 A CN 103000866A
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- ion battery
- lithium ion
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- styrene rubber
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a negative pole material of a lithium ion battery and a manufacturing method of a negative pole of a battery. The negative pole material comprises the following components in percentage by weight: 94-98.5% of graphite, 0-3% of conductive agent and 1.5-6% of binding agent, wherein the binding agent comprises carboxymethyl cellulose and styrene-butadiene rubber at a weight ratio of 1:(1-2), the styrene-butadiene rubber is of a styrene copolymer with the particle size of less than 0.2 mu m, and the pH value of the styrene-butadiene rubber is 6.5-7.5. The negative pole material disclosed by the invention can be used for solving the problems that a negative pole piece has poor adhesion on a cooper foil and poor uniformity, the internal resistance of the battery is higher and the high-temperature discharge performance is poorer; and by adopting the negative pole material and the method, disclosed by the invention, for manufacturing the negative pole piece of the lithium-ion battery, the binding strength of the negative pole piece can be improved, and the internal resistance and high-temperature cyclic discharge performance of the lithium-ion battery manufactured by using the negative pole can be further effectively improved.
Description
Technical field
The invention belongs to the lithium ion battery field, particularly a kind of lithium ion battery negative material and method for manufacturing battery cathode.
Background technology
Lithium ion battery has obtained develop rapidly since earlier 1990s Sony corporation of Japan invention, at present application from little electric current electricity consumption device expand large electric current to, high magnification uses the field, the development trends such as the high magnification of battery, high power capacity, inexpensive and environmental protection are obvious.Concerning lithium ion battery negative material with the binding agent, by the PVDF(Kynoar of initial oiliness) be dissolved in use present aqueous binders CMC(carboxymethyl cellulose in the 1-METHYLPYRROLIDONE) and SBR(butadiene-styrene rubber) etc. be used in combination.But in use there are the following problems for existing binding agent: dispersed low in cathode size of conductive carbon material, adhesive force, caking property and the lack of homogeneity of the negative plate of making on Copper Foil, thus make the internal resistance of battery higher with the high temperature discharge poor-performing.
Summary of the invention
The object of the invention is to overcome the problems referred to above, a kind of lithium ion battery negative material and method for manufacturing battery cathode are provided, to improve the adhesive force of negative material on Copper Foil, to reduce the internal resistance of lithium ion battery and improve the high-temperature lithium ion battery discharge performance.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of lithium ion battery negative material is comprised of following mass percentage content component: graphite 94 ~ 98.5%, conductive agent 0 ~ 3%, binding agent 1.5 ~ 6%; Wherein, binding agent is 1:(1 ~ 2 by mass ratio) carboxymethyl cellulose and butadiene-styrene rubber form, wherein butadiene-styrene rubber be particle diameter less than the styrol copolymer of 0.2 μ m, the pH value of butadiene-styrene rubber is 6.5 ~ 7.5, and the mass percent of butadiene-styrene rubber in negative material is 1 ~ 3%.
Further improvement of the present invention is that described lithium ion battery negative material is comprised of following mass percentage content component: graphite 94 ~ 96%, conductive agent 1 ~ 3%, binding agent 3 ~ 4%.
Further improvement of the present invention is that the molecular weight of described butadiene-styrene rubber is 200000 ~ 300000, and the pH value of butadiene-styrene rubber equals 7, and the mass percent of butadiene-styrene rubber in negative material is 1.5 ~ 2.5%.
Further improvement of the present invention is that the particle diameter of described butadiene-styrene rubber is less than 0.09 μ m, and the pH value equals 7, and the mass percent of butadiene-styrene rubber in negative material is 2.5%.
Further improvement of the present invention is that described conductive agent is acetylene black, conductive black or catalytic pyrolysis material.
Further improvement of the present invention is that described conductive agent is acetylene black, and the mass ratio of graphite, acetylene black, carboxymethyl cellulose and butadiene-styrene rubber is 94:2:1.5:2.5 in the described negative material.
A kind of manufacture method of battery cathode may further comprise the steps:
(1) be 1:(1 ~ 1.2 with lithium ion battery negative material and water according to mass ratio) mix, stir, obtain lithium ion battery cathode slurry;
(2) cathode size that obtains is coated on the Copper Foil, carries out successively drying, compressing tablet and section, obtain the lithium ion battery negative electrode slice.
Further improvement of the present invention is, described stirring is to stir 4 hours with the mixing speed of 1000rpm at normal temperatures.
Further improvement of the present invention is, described drying is 90 ℃ of dryings 1.5 hours.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts particle diameter less than 0.2 μ m, and the pH value is 6.5 ~ 7.5 butadiene-styrene rubber as one of component of lithium ion battery negative binding agent, and butadiene-styrene rubber is preferably styrol copolymer of adhesive property.The particle diameter of butadiene-styrene rubber is unfavorable for when excessive comprising the negative material of binding agent and the strong binding of Copper Foil, and is unfavorable for that battery keeps electrolytical chemically stable at high-temperature field; The particle diameter of butadiene-styrene rubber is less to cause more bounding points, just brings better bond properties; The pH value of butadiene-styrene rubber can affect key and the power of active material in hydrophilic radical in the binding agent and the negative material when excessive or too small, and affects the adhesion strength of active material and Copper Foil.Adopt the adhesion strength of the battery cathode that negative material of the present invention and negative pole manufacture method make obviously to increase, after battery cathode is made into lithium ion battery, the internal resistance of battery obviously descends, and battery rear discharge capacity of 200 circulations under 60 ℃ of high temperature still keeps higher initial discharge capacity level.The invention solves adhesive force and the lack of homogeneity of negative plate on Copper Foil, the problem that causes the higher and high temperature discharge poor-performing of the internal resistance of cell made, the present invention has not only improved the adhesion strength of negative electricity pole piece, has also effectively improved the internal resistance and the high temperature circulation discharge performance that use the lithium ion battery that this negative electricity pole piece makes.
Description of drawings
Fig. 1 is the peel strength figure of the battery cathode of embodiment 8 and Comparative Examples making;
Fig. 2 is the cycle performance figure of the battery made with the battery cathode of embodiment 8 and Comparative Examples making.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment 1
A kind of lithium ion battery negative material, comprise that mass percent is 94% graphite, 2% acetylene black and 4% binding agent, binding agent is that carboxymethyl cellulose and the butadiene-styrene rubber of 1:1.67 forms by mass ratio, wherein butadiene-styrene rubber is that particle diameter is less than the styrol copolymer of 0.09 μ m; the pH value of butadiene-styrene rubber is 7; and the mass percent of butadiene-styrene rubber in negative material is 2.5%; the molecular weight of butadiene-styrene rubber is 250000, and the mass percent of carboxymethyl cellulose in negative material is 1.5% in the binding agent.
A kind of lithium ion battery negative material, comprise that mass percent is 96% graphite, 1% conductive black and 3% binding agent, binding agent is that carboxymethyl cellulose and the butadiene-styrene rubber of 1:1 forms by mass ratio, wherein butadiene-styrene rubber is that particle diameter is less than the styrol copolymer of 0.2 μ m; the pH value of butadiene-styrene rubber is 6.5; and the mass percent of butadiene-styrene rubber in negative material is 1.5%; the molecular weight of butadiene-styrene rubber is 300000, and the mass percent of carboxymethyl cellulose in negative material is 1.5% in the binding agent.
Embodiment 3
A kind of lithium ion battery negative material, comprise that mass percent is 98.5% graphite and 1.5% binding agent, binding agent is that carboxymethyl cellulose and the butadiene-styrene rubber of 1:2 forms by mass ratio, wherein butadiene-styrene rubber is that particle diameter is less than the styrol copolymer of 0.15 μ m; the pH value of butadiene-styrene rubber is 7; and the mass percent of butadiene-styrene rubber in negative material be 1%, and the molecular weight of butadiene-styrene rubber is 200000, and the mass percent of carboxymethyl cellulose in negative material is 0.5% in the binding agent.
Embodiment 4
A kind of lithium ion battery negative material, comprise that mass percent is 94% graphite and 6% binding agent, binding agent is that carboxymethyl cellulose and the butadiene-styrene rubber of 1:1 forms by mass ratio, wherein butadiene-styrene rubber is that particle diameter is less than the styrol copolymer of 0.12 μ m; the pH value of butadiene-styrene rubber is 7.5; and the mass percent of butadiene-styrene rubber in negative material be 3%, and the molecular weight of butadiene-styrene rubber is 230000, and the mass percent of carboxymethyl cellulose in negative material is 3% in the binding agent.
Embodiment 5
A kind of lithium ion battery negative material, comprise that mass percent is 94% graphite, 3% catalytic pyrolysis material and 3% binding agent, binding agent is that carboxymethyl cellulose and the butadiene-styrene rubber of 1:2 forms by mass ratio, wherein butadiene-styrene rubber is that particle diameter is less than the styrol copolymer of 0.05 μ m; the pH value of butadiene-styrene rubber is 7; and the mass percent of butadiene-styrene rubber in negative material is 2%; the molecular weight of butadiene-styrene rubber is 280000, and the mass percent of carboxymethyl cellulose in negative material is 1% in the binding agent.
Embodiment 6
A kind of manufacture method of battery cathode may further comprise the steps:
(1) lithium ion battery negative material and the water with embodiment 2 is that 1:1.2 mixes according to mass ratio, and the mixing speed with 1000rpm stirred 4 hours at normal temperatures, obtained lithium ion battery cathode slurry;
(2) cathode size that obtains is coated on the Copper Foil, carried out drying in 1.5 hours 90 ℃ of dryings, then use the roll squeezer compressing tablet, the die-cutting machine section obtains the lithium ion battery negative electrode slice.
Embodiment 7
A kind of manufacture method of battery cathode may further comprise the steps:
(1) lithium ion battery negative material and the water with embodiment 3 is that 1:1 mixes according to mass ratio, and the mixing speed with 1000rpm stirred 4 hours at normal temperatures, obtained lithium ion battery cathode slurry;
(2) cathode size that obtains is coated on the Copper Foil, carried out drying in 1.5 hours 90 ℃ of dryings, then use the roll squeezer compressing tablet, the die-cutting machine section obtains the lithium ion battery negative electrode slice.
Embodiment 8
A kind of manufacture method of battery cathode may further comprise the steps:
(1) lithium ion battery negative material and the water with embodiment 1 is that 1:1.1 mixes according to mass ratio, and the mixing speed with 1000rpm stirred 4 hours at normal temperatures, obtained lithium ion battery cathode slurry;
(2) cathode size that obtains is coated on the Copper Foil, carried out drying in 1.5 hours 90 ℃ of dryings, then use the roll squeezer compressing tablet, die-cutting machine is cut into slices, and obtains the lithium ion battery negative electrode slice of length * wide * thick=111mm * 61mm * 138 μ m.
The battery cathode that battery cathode and the Comparative Examples of embodiment 8 making are made is tested respectively its peel strength.Lithium ion battery negative material in the Comparative Examples is identical with the composition of embodiment 1, distinguishes particle diameter into butadiene-styrene rubber greater than 0.3 μ m, and the pH value of butadiene-styrene rubber is 7.8, and it is identical with embodiment 8 to make the method for battery cathode in the Comparative Examples.Use JWFU peel bond strength meter test peel strength value.Fig. 1 is the peel strength figure of embodiment 8 and the Comparative Examples battery cathode of making, and Fig. 1 shows, the adhesion strength of lithium ion battery negative electrode is brought up to the 6200gf/mm2 of embodiment 8 by the 4000-5000gf/mm2 of Comparative Examples, and adhesion strength is significantly increased.
The battery cathode that battery cathode and the Comparative Examples of embodiment 8 making are made is made into respectively lithium ion battery, tests both cell voltage, internal resistance and cycle performances.Wherein the manufacture method of lithium ion battery is:
1. the preparation of anode electrode of lithium ion battery sheet
According to mass ratio LiFePO4: acetylene black: the PVDF(Kynoar): 1-METHYLPYRROLIDONE=91:3:6:120 is configured to anode sizing agent, be coated in after stirring on the thick aluminium foil of 15 μ m, then 100 ℃ of dryings are 1.5 hours, the roller compressing tablet, die-cutting machine is cut into slices, and obtains the anode electrode of lithium ion battery sheet of length * wide * thick=109mm * 59mm * 164 μ m.
2. the preparation of lithium ion battery:
The polypropylene screen barrier film of the based lithium-ion battery positive plate that above-mentioned steps is made, the negative plate made from embodiment 8 and Comparative Examples and thick 25 μ m stacks successively according to the order of positive plate, barrier film, negative plate, makes the electrode cores of lithium ion battery.This electrode cores is put into lithium ion battery aluminum plastic film shell, then inject 38g electrolyte, the finally sealed battery case is made lithium ion battery.The composition of electrolyte is: the LiPF of 1mol/L
6(electrolytic salt) is dissolved in according to volume ratio ethylene carbonate (EC): dimethyl carbonate (DMC): in the mixed solvent that diethyl carbonate (DEC)=1:1:1 mixes.
Make respectively two groups of each 8 batteries with the battery cathode that embodiment 8 and Comparative Examples are made, to two Battery pack test battery voltage and internal resistances, the result lists in the table 1; And two Battery packs are put into high low temperature cabinet be warming up to 60 ℃, then carry out the cycle performance test, choose a battery data of cycle performance optimum in every group, drafting pattern 2.Use day to put the internal resistance of internal resistance test device test battery, use in Wuhan Sai Aisi LHS-B5V20A test cabinet and the high low temperature cabinet battery is carried out the test of high temperature cyclic performance: battery charges to 3.6V with 0.5C, 3.6V constant voltage charge to electric current less than 0.01C, then to 2.0V, so circulation obtains the cycle performance of battery data to battery with the 1C multiplying power discharging.
Voltage and the internal resistance of the battery that the battery cathode that table 1 is made for embodiment 8 and Comparative Examples is made, after table 1 shows that the battery cathode of embodiment 8 and Comparative Examples making is made into lithium ion battery, the internal resistance of battery is on average dropped to the 5.75m Ω of embodiment 8 by the 7.57m Ω of Comparative Examples, descend obviously, and the average voltage difference of two Battery packs is little.
Voltage and the internal resistance of the battery that the battery cathode that table 1 embodiment 8 and Comparative Examples are made is made
Fig. 2 is the cycle performance figure of the battery made with the battery cathode of embodiment 8 and Comparative Examples making, Fig. 2 shows, the battery cathode that embodiment 8 makes make battery discharge capacity after 200 circulations of 60 ℃ of high temperature still keep 85.43% of initial discharge capacity, and battery discharge capacity after 200 circulations of 60 ℃ of high temperature that the battery cathode that Comparative Examples is made is made only keeps 58.16% of initial discharge capacity, the battery made from Comparative Examples namely drops to below 50% of initial capacity 208 circulation time discharge capacities, and the battery that adopts embodiment 8 to make just drops to below 50% of initial capacity 286 circulation time discharge capacities, illustrates that ion cathode material lithium and negative pole manufacture method that the present invention proposes can increase substantially battery performance.
In sum, adopt negative material of the present invention to make the lithium ion battery negative electrode slice, not only improved the adhesion strength of negative electricity pole piece, also effectively improved the internal resistance and the high temperature circulation discharge performance that use the lithium ion battery that this negative electrode makes.
Claims (9)
1. a lithium ion battery negative material is characterized in that: be comprised of following mass percentage content component: graphite 94 ~ 98.5%, conductive agent 0 ~ 3%, binding agent 1.5 ~ 6%;
Wherein, binding agent is 1:(1 ~ 2 by mass ratio) carboxymethyl cellulose and butadiene-styrene rubber form, wherein butadiene-styrene rubber be particle diameter less than the styrol copolymer of 0.2 μ m, the pH value of butadiene-styrene rubber is 6.5 ~ 7.5, and the mass percent of butadiene-styrene rubber in negative material is 1 ~ 3%.
2. lithium ion battery negative material according to claim 1, it is characterized in that: described lithium ion battery negative material is comprised of following mass percentage content component: graphite 94 ~ 96%, conductive agent 1 ~ 3%, binding agent 3 ~ 4%.
3. lithium ion battery negative material according to claim 1 and 2, it is characterized in that: the molecular weight of described butadiene-styrene rubber is 200000 ~ 300000, the pH value of butadiene-styrene rubber equals 7, and the mass percent of butadiene-styrene rubber in negative material is 1.5 ~ 2.5%.
4. lithium ion battery negative material according to claim 1 and 2, it is characterized in that: the particle diameter of described butadiene-styrene rubber is less than 0.09 μ m, and the pH value equals 7, and the mass percent of butadiene-styrene rubber in negative material is 2.5%.
5. lithium ion battery negative material according to claim 1 and 2, it is characterized in that: described conductive agent is acetylene black, conductive black or catalytic pyrolysis material.
6. lithium ion battery negative material according to claim 1, it is characterized in that: described conductive agent is acetylene black, the mass ratio of graphite, acetylene black, carboxymethyl cellulose and butadiene-styrene rubber is 94:2:1.5:2.5 in the described negative material.
7. the manufacture method of a battery cathode is characterized in that: may further comprise the steps:
(1) be 1:(1 ~ 1.2 with the described lithium ion battery negative material of any one and water among the claim 1-6 according to mass ratio) mix, stir, obtain lithium ion battery cathode slurry;
(2) cathode size that obtains is coated on the Copper Foil, carries out successively drying, compressing tablet and section, obtain the lithium ion battery negative electrode slice.
8. method for manufacturing battery cathode according to claim 7 is characterized in that: described stirring was stirred 4 hours for the mixing speed with 1000rpm at normal temperatures.
9. method for manufacturing battery cathode according to claim 7 is characterized in that: described drying is for 90 ℃ of dryings 1.5 hours.
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| CN2012105135330A CN103000866A (en) | 2012-12-03 | 2012-12-03 | Negative pole material of lithium ion battery and manufacturing method of negative pole of battery |
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| CN2012105135330A CN103000866A (en) | 2012-12-03 | 2012-12-03 | Negative pole material of lithium ion battery and manufacturing method of negative pole of battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600318A (en) * | 2015-02-05 | 2015-05-06 | 天津市捷威动力工业有限公司 | Modified CMC and gel battery thereof |
| CN109004217A (en) * | 2018-07-19 | 2018-12-14 | 湖北宇隆新能源有限公司 | A kind of cathode of lithium battery slice prescription |
| CN114242934A (en) * | 2021-12-16 | 2022-03-25 | 珠海冠宇电池股份有限公司 | Electrode assembly and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237526A (en) * | 2010-04-29 | 2011-11-09 | 上海比亚迪有限公司 | Lithium ion battery cathode slurry, cathode and battery |
| WO2012090669A1 (en) * | 2010-12-28 | 2012-07-05 | Jsr株式会社 | Binder composition for electrodes, electrode slurry, electrode, electrochemical device, and production method and storage method of binder composition for electrodes |
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2012
- 2012-12-03 CN CN2012105135330A patent/CN103000866A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237526A (en) * | 2010-04-29 | 2011-11-09 | 上海比亚迪有限公司 | Lithium ion battery cathode slurry, cathode and battery |
| WO2012090669A1 (en) * | 2010-12-28 | 2012-07-05 | Jsr株式会社 | Binder composition for electrodes, electrode slurry, electrode, electrochemical device, and production method and storage method of binder composition for electrodes |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600318A (en) * | 2015-02-05 | 2015-05-06 | 天津市捷威动力工业有限公司 | Modified CMC and gel battery thereof |
| CN104600318B (en) * | 2015-02-05 | 2017-05-10 | 天津市捷威动力工业有限公司 | Modified CMC and gel battery thereof |
| CN109004217A (en) * | 2018-07-19 | 2018-12-14 | 湖北宇隆新能源有限公司 | A kind of cathode of lithium battery slice prescription |
| CN114242934A (en) * | 2021-12-16 | 2022-03-25 | 珠海冠宇电池股份有限公司 | Electrode assembly and application thereof |
| CN114242934B (en) * | 2021-12-16 | 2024-05-17 | 珠海冠宇电池股份有限公司 | Electrode assembly and application thereof |
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Application publication date: 20130327 |