CN102185130B - Preparation method for cathode of lithium ion battery - Google Patents

Preparation method for cathode of lithium ion battery Download PDF

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Publication number
CN102185130B
CN102185130B CN2011100585223A CN201110058522A CN102185130B CN 102185130 B CN102185130 B CN 102185130B CN 2011100585223 A CN2011100585223 A CN 2011100585223A CN 201110058522 A CN201110058522 A CN 201110058522A CN 102185130 B CN102185130 B CN 102185130B
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graphite
cmc
rotation
revolution
cathode
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CN102185130A (en
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胡泽军
汪怡飞
官彬
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Anhui Fengchi New Energy Technology Co ltd
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ZHEJIANG HALISE NEW ENERGY Ltd
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    • YGENERAL 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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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention belongs to the production field of lithium ion batteries and particularly relates to a preparation method for a cathode of a lithium ion battery. The method provided by the invention comprises the following steps: weighing graphite, CMC (Carboxy Methyl Cellulose), SBR (Styrene Butadiene Rubber) latex and deionized water in proportion; adding a part of the graphite to the CMC, and carrying out the premixing processing, wherein the weight of the premixed graphite is 2-3 times that of the CMC; adding the deionized water to a vacuum agitating vessel; starting the autorotation; gradually adding the mixed powder of the preprocessed CMC and graphite; stopping the autorotation after no powder exists; vacuumizing; starting the revolution and the autorotation; agitating; gradually adding the residual graphite to the vacuum agitating vessel; starting the revolution and the autorotation; stopping the agitating after no powder exists; vacuumizing; starting the revolution and the autorotation; agitating; adding the SBR latex to the vacuum agitating vessel; vacuumizing; starting the revolution and the autorotation; agitating; adding the residual deionized water to adjust the viscosity of the slurry; and sieving and discharging after continuously agitating. Compared with the conventional preparation method, the preparation method provided by the invention has the characteristics of low energy consumption, high production efficiency, good product quality and the like.

Description

A kind of preparation method for cathode of lithium ion battery
Technical field
The invention belongs to the lithium ion battery production field, relate to specifically the preparation method for cathode of lithium ion battery of CMC system.
Background technology
Blending process is actually the various compositions in the slurry is mixed by standard proportional, is modulated into slurry, is beneficial to even coating, guarantees the consistency of pole piece.During lithium ion battery is produced at present, the cathode blending time is longer, especially adopt the batching of CMC system, when preparation CMC solution, need to stir 2-3 hour, and shelved 5-8 hour, one barrel of negative material is prepared and is often wanted more than 10 hour, has the technological process of conventional cathode blending method now as shown in Figure 1, and Main Problems has the following aspects:
(1) have influence on the utilization rate of equipment, an equipment can only use 2 circulations every day;
(2) the CMC solution preparation stirred 2-3 hour, and the CMC strand is cut more, and CMC not necessarily can dissolve fully, and the slurry of preparation easily precipitates;
(3) 2-3 hour of the stirring of preparation CMC solution, energy resource consumption was many.
By top described, can find out that present conventional cathode blending method also has further improved necessity and needs.Existing report has is absorbed in cathode formula, provides a kind of graphite water-base cathode formula such as publication number for CN 101604742A, still, does not also have about the report of cathode blending method. 
Summary of the invention
The problems referred to above for the prior art existence, the object of the invention is to work in addition thinking, a kind of preparation method for cathode of lithium ion battery is provided, improve the efficient of cathode blending, reduce energy resource consumption, Improving The Quality of Products is in the hope of improving the cathode blending problem that solves, and then promote the progress of whole lithium electricity industry technology, support the energy-saving and emission-reduction plan of country.
The objective of the invention is to be implemented by the following technical programs:
A kind of preparation method for cathode of lithium ion battery comprises the steps:
A. get the raw materials ready: take by weighing in proportion graphite, CMC, SBR latex and deionized water,
The b.CMC preliminary treatment: add a part of graphite and carry out the premix processing in CMC, the graphite of premix is CMC weight 2-3 times,
C. the deionized water of the ionized water total weight that will account for more than 90% adds in the vacuum stirring bucket, opens rotation, and the mixed powder of pretreated CMC and graphite is progressively added, after without powder, stop rotation, vacuumize, open revolution and rotation, stir and stop after 10-15 minute stirring
D. remaining graphite is progressively added in the vacuum stirring bucket, open revolution and rotation, stop to stir after without powder, vacuumize, unlatching is revolved round the sun and rotation, stir after 2.5-3 hour to stop to stir,
E. with in the SBR latex adding vacuum stirring bucket, vacuumize, unlatching revolution and rotation behind the stirring 30min, add the viscosity that remaining deionized water is adjusted slurry, the discharging of sieving behind the continuation stirring 20-30min.
The CMC full name is sodium carboxymethylcellulose, is absorbent material very easily, when dissolving separately, can become the dough formula, the attached one-tenth one glue shell of outer bag, and internal layer is the CMC powder, therefore extremely difficulty scatter; When stirring CMC solution, need high rotating speed, and under high rotating speed, thereby grown the strand of CMC and just can be cut off and can cause slurry sediment the time for this reason; And graphite very easily spreads after meeting water, always produces one to the power of outdiffusion, and this specific character that for this reason can take full advantage of graphite is adjusted the dissolution mechanism of CMC, accelerates the preparation of CMC solution.The inventor studies discovery, after processing with graphite and CMC premix first, add again deionized water for stirring to, can greatly shorten the time of cathode blending process, reduce the cathode blending energy consumption, and the cathode size physical property of preparation is better than the cathode size that existing conventional cathode blending method obtains, and the cathode size that electric property and conventional cathode blending method obtain is suitable.
As preferably, the method according to a kind of lithium ion battery negative batching of the present invention wherein, among the described step a is: graphite 100 weight portions, CMC 2-3 weight portion, SBR latex 4-5 weight portion, deionized water 145-148 weight portion in proportion.In the prescription, graphite is negative electrode active material, and SBR latex, full name are carboxylic styrene butadiene latexs, is aqueous binder, and CMC is antisettling agent, and deionized water is diluent.
As preferably, according to the method for a kind of lithium ion battery negative batching of the present invention, wherein, be evacuated among described step c, steps d and the step e vacuum degree for-0.1MPa to-0.08MPa.The vacuum stirring effect that vacuum degree control can obtain in this scope.
As preferably, according to the method for a kind of lithium ion battery negative batching of the present invention, wherein, described steps d is: remaining graphite is progressively added in the vacuum stirring bucket, open revolution and rotation, the revolution frequency is 25Hz, and rotation frequency is 30Hz, after without powder, stop to stir, vacuumize, open revolution and rotation, the revolution frequency is 30Hz, rotation frequency is 35Hz, stirs after 2.5-3 hour to stop to stir.Production efficiency, energy consumption optimum.
As preferably, according to the method for a kind of lithium ion battery negative batching of the present invention, wherein, among the described step e: add remaining deionized water and adjust the viscosity of slurry to 1800-2500mPa.s.Viscosity is controlled at this scope, is beneficial to follow-up coating.
The present invention compared with prior art has the following advantages:
(1) energy resource consumption is low, relatively save more than 30% than conventional cathode blending method energy consumption,
(2) production efficiency improves, and utilization rate of equipment and installations is by being increased to every day 5-6 time every day for 2-3 time,
(3) product quality promotes, and especially physical property is better than conventional cathode blending method greatly.
Description of drawings
Fig. 1 is the process chart of existing conventional preparation method for cathode of lithium ion battery.
Fig. 2 is the process chart of preparation method for cathode of lithium ion battery of the present invention.
Fig. 3 is the coulombic efficiency test curve figure after cathode size that conventional cathode blending method and cathode blending method of the present invention obtain is assembled into cylinder LiFePO4 IFR18650-1300mAh battery.
Fig. 4 is the cycle performance of battery test collection of illustrative plates after cathode size that conventional cathode blending method and cathode blending method of the present invention obtain is assembled into cylinder LiFePO4 IFR18650-1300mAh battery.
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation and/or change that the present invention is made all will fall into protection range of the present invention.
In the present invention, if not refer in particular to, all equipment and raw material etc. all can be buied from market or the industry is commonly used.Method among the following embodiment if no special instructions, is the conventional method of this area.
Capital equipment and raw material:
The vacuum stirring bucket, specification 100L, Guangzhou good luck machinery plant;
The gap coating machine, model XTB8-322E, Shenzhen Xinyuren Technology Co., Ltd.;
Twin rollers, model LDHY600-N60, Xingtai Naknor Pole-Piece Rolling Equipment Co., Ltd.;
The experiment checkout equipment, model BTS0305C8, Ningbo Bate Technology Co., Ltd.;
Positive electrode: SLFP-PD60, Tianjin Si Telan company.
Embodiment 1:
(1). negative material and weight proportion thereof:
Graphite: the CGP-6 of Liaoning Hongguang Science ﹠ Technology Group Co., Ltd., 100 parts;
CMC:BVH8,2 parts;
SBR latex: 50%, 4 part of SBR styrene-butadiene latex;
Deionized water: 145 parts.
(2). the following (see figure 2) of the process of cathode blending:
A. take by weighing 2 parts of CMC, take by weighing again 6 parts of graphite, add simultaneously in the stainless steel cask, stir about 2min with little mixer, stir, be as the criterion substantially can't see CMC powder in heaps.
B. take by weighing 130 parts of water and be added in the vacuum stirring bucket, and check whether bucket leaks vacuum etc., adjusts the stirring arm position, avoids charge door.Open rotation, frequency 30Hz makes deionized water present shuttling movement in bucket.
C. mixed CMC+ graphite powder is progressively added in the vacuum stirring bucket with funnel, observes stirring, after without powder, stop rotation, after the siccative of bucket wall is scraped, be evacuated to-0.1MPa about.Open and stir, revolution frequency 30Hz, rotation frequency 35Hz stops to stir behind the stirring 10min.
D. remaining graphite progressively is added in the vacuum stirring bucket, opens and stir, revolution frequency 25Hz, rotation frequency 30Hz, first stirring at low speed after without powder, stops to stir.Be evacuated to-0.1MPa, open stir, revolution frequency 30Hz, rotation frequency 35Hz stirs and stops stirring after 2.5 hours, and scraper is once in the whipping process.
E. SBR latex is added in the vacuum stirring bucket, is evacuated to-0.1MPa, open and stir, revolution frequency 30Hz, rotation frequency 35Hz is behind the stirring 30min, viscosimetric, and the viscosity of adjusting slurry with remaining deionized water is to 1800-2500mPa.s is crossed 150 mesh sieve dischargings after continuing to stir 30min.The cathode size quantitative measurement that obtains the results are shown in Table 1.
According to this area current techique assembled battery, take cylinder LiFePO4 IFR18650-1300mAh battery as example, carry out electrical performance testing, the coulombic efficiency test result sees Table 2 and Fig. 3, and the cycle performance of battery test result is seen Fig. 4.
The coulombic efficiency test: take cylinder LiFePO4 IFR18650-1300mAh battery as example, method of testing is: first step 65mA, constant current charge 60min; Second step 130mA, constant current charge 120min; The 3rd step 260mA, constant current charge 240min, constant voltage 3.8V cut-off current 13mA; The 4th step was shelved 10min; The 5th step 260mA, constant-current discharge is to 2V; In the 6th step, shelve 10min; In the 7th step, the 260mA constant current charge is to 3.8V.
Coulombic efficiency computational methods: be coulombic efficiency except former total charging capacity of four steps with the 5th step discharge capacity.
Energy consumption in the cathode blending process sees Table 3.
Embodiment 2:
(1). negative material and weight proportion thereof:
Graphite: the CGP-6 of Liaoning Hongguang Science ﹠ Technology Group Co., Ltd., 100 parts;
CMC:BVH8,3 parts;
SBR latex: 50%, 5 part of SBR styrene-butadiene latex;
Deionized water: 148 parts.
(2). the following (see figure 2) of the process of cathode blending:
A. take by weighing 3 parts of CMC, take by weighing again 6 parts of graphite, add simultaneously in the stainless steel cask, stir about 2min with little mixer, stir, be as the criterion substantially can't see CMC powder in heaps.
B. take by weighing 134 parts of water and be added in the vacuum stirring bucket, and check whether bucket leaks vacuum etc., adjusts the stirring arm position, avoids charge door.Open rotation, frequency 30Hz makes deionized water present shuttling movement in bucket.
C. mixed CMC+ graphite powder is progressively added in the vacuum stirring bucket with funnel, observe stirring, after without powder, stop rotation, after the siccative of bucket wall is scraped, be evacuated to-0.08MPa.Open and stir, revolution frequency 30Hz, rotation frequency 35Hz stops to stir behind the stirring 15min.
D. remaining graphite progressively is added in the vacuum stirring bucket, opens and stir, revolution frequency 25Hz, rotation frequency 30Hz, first stirring at low speed after without powder, stops to stir.Be evacuated to-0.08MPa, open stir, revolution frequency 30Hz, rotation frequency 35Hz stirs and stops stirring after 3 hours, and scraper is once in the whipping process.
E. SBR latex is added in the vacuum stirring bucket, be evacuated to-0.08MPa, open and stir, revolution frequency 30Hz, rotation frequency 35Hz, behind the stirring 30min, viscosimetric, and the viscosity of adjusting slurry with remaining deionized water is to 1800-2500mPa.s, crosses 150 mesh sieve dischargings after continuing to stir 20min.The cathode size quantitative measurement that obtains the results are shown in Table 1.
According to this area current techique assembled battery, take cylinder LiFePO4 IFR18650-1300mAh battery as example, carry out electrical performance testing, the coulombic efficiency test result sees Table 2 and Fig. 3, and the cycle performance of battery test result is seen Fig. 4.
The enclosed pasture efficiency test: take cylinder LiFePO4 IFR18650-1300mAh battery as example, method of testing is: first step 65mA, constant current charge 60min; Second step 130mA, constant current charge 120min; The 3rd step 260mA, constant current charge 240min, constant voltage 3.8V cut-off current 13mA; The 4th step was shelved 10min; The 5th step 260mA, constant-current discharge is to 2V; In the 6th step, shelve 10min; In the 7th step, the 260mA constant current charge is to 3.8V.
Coulombic efficiency computational methods: be coulombic efficiency except former total charging capacity of four steps with the 5th step discharge capacity.
Energy consumption in the cathode blending process sees Table 3.
Comparative example 1 conventional batching
(1). negative material and weight proportion thereof:
With embodiment 1.
(2). the following (see figure 1) of the process of cathode blending:
A. take by weighing 130 parts of water and be added in the vacuum stirring bucket, and check whether bucket leaks vacuum etc., adjusts the stirring arm position, avoids charge door.Open rotation, frequency 30Hz makes deionized water present shuttling movement in bucket.
B. 2 parts of CMC are progressively added in the vacuum stirring bucket with funnel, observe stirring, after without powder, stop rotation, after the siccative of bucket wall is scraped, be evacuated to-0.09MPa.Open to stir, revolution frequency 30Hz, rotation frequency 35Hz stirs and stops stirring after 2 hours.Then shelved 5 hours.
C. graphite progressively is added in the vacuum stirring bucket, opens and stir, revolution frequency 25Hz, rotation frequency 30Hz, first stirring at low speed after without powder, stops to stir.Be evacuated to-0.09MPa, open stir, revolution frequency 30Hz, rotation frequency 35Hz stirs and stops stirring after 2.5 hours, and scraper is once in the whipping process.
D. SBR latex is added in the vacuum stirring bucket, be evacuated to-0.09MPa, open and stir, revolution frequency 30Hz, rotation frequency 35Hz, behind the stirring 30min, viscosimetric, and the viscosity of adjusting slurry with remaining deionized water is to 1800-2500mPa.s, crosses 150 mesh sieve dischargings after continuing to stir 30min.The cathode size quantitative measurement that obtains sees Table 1.
According to this area current techique assembled battery, take cylinder LiFePO4 IFR18650-1300mAh battery as example, carry out electrical performance testing, the coulombic efficiency test result sees Table 2 and Fig. 3, and the cycle performance of battery test result is seen Fig. 4.
The enclosed pasture efficiency test: take cylinder LiFePO4 IFR18650-1300mAh battery as example, method of testing is: first step 65mA, constant current charge 60min; Second step 130mA, constant current charge 120min; The 3rd step 260mA, constant current charge 240min, constant voltage 3.8V cut-off current 13mA; The 4th step was shelved 10min; The 5th step 260mA, constant-current discharge is to 2V; In the 6th step, shelve 10min; In the 7th step, the 260mA constant current charge is to 3.8V.
Coulombic efficiency computational methods: be coulombic efficiency except former total charging capacity of four steps with the 5th step discharge capacity.
Energy consumption in the cathode blending process sees Table 3.
Figure 942242DEST_PATH_IMAGE002
As can be seen from Table 3, the present invention's energy consumption in blending process saves 30.67% relatively.
Above preferred embodiment just is used for description and interpretation content of the present invention, does not consist of the restriction to content of the present invention.Although the inventor has done in more detail the present invention and has enumerated, but, the content that those skilled in the art discloses according to summary of the invention part and embodiment, can make various modifications or/and to replenish or adopt similar mode to substitute be obvious to described specific embodiment, and can realize technique effect of the present invention, therefore, give unnecessary details no longer one by one herein.The term that occurs among the present invention is used for elaboration and the understanding to technical solution of the present invention, is not construed as limiting the invention.

Claims (4)

1. a preparation method for cathode of lithium ion battery is characterized in that, described preparation method for cathode of lithium ion battery comprises the steps:
A. get the raw materials ready: take by weighing in proportion graphite, CMC, SBR latex and deionized water, describedly be in proportion: graphite 100 weight portions, CMC 2-3 weight portion, SBR latex 4-5 weight portion, deionized water 145-148 weight portion,
The b.CMC preliminary treatment: add a part of graphite and carry out the premix processing in CMC, the graphite of premix is CMC weight 2-3 times,
C. the deionized water of the ionized water total weight that will account for more than 90% adds in the vacuum stirring bucket, opens rotation, and the mixed powder of pretreated CMC and graphite is progressively added, after without powder, stop rotation, vacuumize, open revolution and rotation, stir and stop after 10-15 minute stirring
D. remaining graphite is progressively added in the vacuum stirring bucket, open revolution and rotation, stop to stir after without powder, vacuumize, unlatching is revolved round the sun and rotation, stir after 2.5-3 hour to stop to stir,
E. with in the SBR latex adding vacuum stirring bucket, vacuumize, unlatching revolution and rotation behind the stirring 30min, add the viscosity that remaining deionized water is adjusted slurry, the discharging of sieving behind the continuation stirring 20-30min.
2. a kind of preparation method for cathode of lithium ion battery according to claim 1 is characterized in that, be evacuated among described step c, steps d and the step e vacuum degree for-0.1MPa to-0.08Mpa.
3. a kind of preparation method for cathode of lithium ion battery according to claim 1, it is characterized in that described steps d is: remaining graphite is progressively added in the vacuum stirring bucket, open revolution and rotation, the revolution frequency is 25Hz, rotation frequency is 30Hz, stops to stir after without powder, vacuumizes, open revolution and rotation, the revolution frequency is 30Hz, and rotation frequency is 35Hz, stirs after 2.5-3 hour to stop to stir.
4. a kind of preparation method for cathode of lithium ion battery according to claim 1 is characterized in that, among the described step e: add remaining deionized water and adjust the viscosity of slurry to 1800-2500mPa.s.
CN2011100585223A 2011-03-11 2011-03-11 Preparation method for cathode of lithium ion battery Expired - Fee Related CN102185130B (en)

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Publication number Priority date Publication date Assignee Title
CN103022433A (en) * 2012-11-23 2013-04-03 彩虹集团公司 Method for preparing lithium battery slurry
CN104466173A (en) * 2013-09-16 2015-03-25 四川英志新能源股份有限公司 Anode water system stirring process of LFP (lithium ferric phosphate) battery manufacturing process
CN104201331A (en) * 2014-07-29 2014-12-10 江西世纪长河新电源有限公司 Pole piece of negative pole in lithium ion secondary battery
CN108448074A (en) * 2018-02-05 2018-08-24 合肥国轩高科动力能源有限公司 A kind of preparation method of lithium ion battery anode slurry

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CN101262077A (en) * 2008-04-29 2008-09-10 上海德朗能电池有限公司 A high-capacity secure 26650 lithium ion battery and its making method
CN101393985A (en) * 2007-09-21 2009-03-25 深圳市比克电池有限公司 Negative pole material, preparation for battery and battery manufactured by the negative pole material
CN101459237A (en) * 2007-12-10 2009-06-17 深圳市比克电池有限公司 Battery cathode slurry, preparation and battery produced by the cathode slurry

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US6589299B2 (en) * 2001-02-13 2003-07-08 3M Innovative Properties Company Method for making electrode
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CN101393985A (en) * 2007-09-21 2009-03-25 深圳市比克电池有限公司 Negative pole material, preparation for battery and battery manufactured by the negative pole material
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