CN100547828C - Lithium ion battery anode glue size preparation method, positive plate and lithium ion battery - Google Patents

Lithium ion battery anode glue size preparation method, positive plate and lithium ion battery Download PDF

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Publication number
CN100547828C
CN100547828C CNB2005100205587A CN200510020558A CN100547828C CN 100547828 C CN100547828 C CN 100547828C CN B2005100205587 A CNB2005100205587 A CN B2005100205587A CN 200510020558 A CN200510020558 A CN 200510020558A CN 100547828 C CN100547828 C CN 100547828C
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solvent
time
lithium ion
ion battery
mixing
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CN1835260A (en
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黄加军
张志文
邵戈
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Zhengzhou Bike Battery Co Ltd
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Shenzhen Bak Battery Co 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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Abstract

The present invention discloses a kind of lithium ion battery anode glue size preparation method, comprises the steps: the anodal mixing of materials with weighing; Add solvent and stir in mixed anodal material and make anode sizing agent, the adding of described solvent divides at least twice to carry out.The effect that the present invention is useful is: adopt method in batches to add solvent, avoid solvent once to add after the shortcoming of the slurry that long-time stirring still can't obtain to mix, add in batches, mix gradually, slurry more easy to control stirs the concrete situation in each stage, reaches the effect of getting twice the result with half the effort, and makes solvent more even with mixing of material, the slurry that makes has good stable, places not stratified after 24 hours.

Description

Lithium ion battery anode glue size preparation method, positive plate and lithium ion battery
[technical field]
The present invention relates to materials chemistry field and high-energy battery technology, be specifically related to lithium ion battery anode glue size preparation method, positive plate and lithium ion battery.
[background technology]
After proposing " rocking chair battery " notion (RCB) in 1980, Sony corporation of Japan and Sanyo are respectively at beginning the lithium rechargeable battery practical research in 1985 and 1988, because lithium rechargeable battery has the operating voltage height, specific energy is big, self discharge is little, temperature limit is wide, stable operating voltage, outstanding features such as storage life is long, countries in the world all to lithium rechargeable battery at communication field, portable type electronic product, electric motor car, with the application table of aspects such as space flight and aviation great interest and enthusiasm are shown, and have carried out continuous exploration and improvement at the performance and the manufacturing process of lithium rechargeable battery.
In the last few years, the lithium ion battery manufacturing technology had had very much progress, made that model for example is the capacity of 18650 cylindrical battery, brings up to present 2400mAh from initial 1200mAh.But with regard to anode sizing agent preparation technology, most of company all continues to use traditional preparation technology, this technology is played glue with bonding agent and solvent earlier, then the colloid of preparation is added in the mixture of positive electrode active materials and conductive agent and stir, vacuumize after stirring, discharging then, sieve, make anode sizing agent.This preparation technology has following shortcoming: 1) uniformity of slurry is bad; 2) stability of slurry is bad, slurry layering easily after placement a period of time.
[summary of the invention]
The object of the present invention is to provide a kind of anode sizing agent that makes acquisition evenly and the lithium ion battery anode glue size preparation method who has good stability, and the positive plate and the lithium ion battery that adopt this method to make.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of lithium ion battery anode glue size preparation method comprises the steps:
1) with the anodal mixing of materials of weighing;
2) add solvent and stir and make anode sizing agent in mixed anodal material, the adding of described solvent divides at least twice to carry out.
Preferably, in described step 2) in solvent divide 2~4 addings.
Most preferably, in described step 2) in solvent divide 3 addings.
Solvent divides and adds for 3 times fashionablely, and each time addition preferably adopts such method of salary distribution: solvent adding amount is 8%~12% of a solvent total amount for the first time, and addition is 50%~65% of a total amount for the second time, adds remaining solvent for the third time.
In the process that adds solvent, can use blender to stir, solvent divides 3 times to add fashionable, the stirring frequency of blender and the optimal process parameter of mixing time are: blender revolution frequency was 8~15Hz after solvent added for the first time, and mixing time is 0.5~2 hour; Blender revolution frequency was 15~30Hz after solvent added for the second time, and mixing time is 0.5~1.5 hour; Blender revolution frequency was 35~40Hz after solvent added for the third time, and rotation frequency is 35~40Hz, and mixing time is 3~5 hours.
Described anodal material can comprise positive electrode active materials, conductive agent and bonding agent etc.
The preferred employing grinds the mixing that machinery carries out anodal material in described step 1), makes anodal material levigate and mix.The described machinery that grinds can be selected ball mill for use.
When selecting for use ball mill to carry out mixing of materials, its optimal process parameter is ball milling frequency 30~70Hz, ratio of grinding media to material 1: 2~1: 1.5, milling time 1.5~4 hours.
The present invention also provides a kind of positive plate of the lithium ion battery that has used said method in the anode sizing agent preparation process and the lithium ion battery with this positive plate.
Adopt technique scheme, in conjunction with the following embodiment that will describe in detail, beneficial technical effects of the present invention is: 1) adopt method in batches to add solvent, avoid solvent once to add after the shortcoming of the slurry that long-time stirring still can't obtain to mix, add in batches, mix gradually, slurry more easy to control stirs the concrete situation in each stage, reach the effect of getting twice the result with half the effort, make solvent more even with mixing of material, the slurry that makes has good stable, places not stratified after 24 hours.2) preferably dividing 2~4 times, preferably add solvent 3 times, is that abundant balance considers that explained hereafter cycle and slurry mix the result of degree, can reach the best combination of efficient and effect; 3) the preferred stirring technique parameter of institute obtains through testing repeatedly, can make solvent and material reach splendid mixed effect; 4) in mixing of materials technology, adopt and grind machinery and stir, the levigate and abundant mixing of material can be improved the stock quality that makes; 5) preferred ball milling is as batch mixing machinery, its technology maturation, and the operability of product is good, easy to use and control; 6) adopt the hybrid parameter of designing at ball-milling technology, the fineness and the mixability of material can be controlled at optimum state.
The present invention is described in further detail below by embodiment.
[embodiment]
The invention provides a kind of lithium ion battery anode glue size preparation method, comprise the steps:
1) with the anodal mixing of materials of weighing.Described anodal material is meant the required various raw materials of preparation lithium ion battery anode glue size, comprises positive electrode active materials, conductive agent and bonding agent etc.Preferred in this step the employing grinds machinery, and for example ball mill carries out the mixing of anodal material, can when reaching the mixing purpose anodal improved grinding be arrived certain fineness like this, improves the quality of the slurry that makes.When selecting for use ball mill to carry out mixing of materials, its optimal process parameter is ball milling frequency 30~70Hz, ratio of grinding media to material 1: 2~1: 1.5, milling time 1.5~4 hours.In this technology, ratio of grinding media to material can not be crossed low or too high, and ratio of grinding media to material is low excessively, and (<1: 2), expect that many balls are few, it is inhomogeneous that material is mixed, and ball milling is also inhomogeneous; Ratio of grinding media to material too high (>1: 1.5) ball is too much, easily material grind meticulously, overbreak, and easily ball is smashed.The ball milling frequency can not be too high or too low, frequency too high (>70Hz), centripetal force is excessive, ball is adjacent to casing wall and wall moves together, can not be well material be mixed; Underfrequency (<30Hz), centripetal force is too small, material well can not be mixed equally, and preferably preferred 50Hz under this frequency, can fall down when ball rises to peak automatically, plays best mixed effect.The degree that mixes of ball milling time effects material, ball milling overlong time (>4 hours) can be ground material meticulously, destroys the structure of active ingredient; The ball milling time too short (<1.5 hours) does not have the effect of mixing, material can not be mixed.
2) add solvent and stir and make anode sizing agent in mixed anodal material, the adding of described solvent divides at least twice to carry out.In this step solvent being added in batches is to reach adhesive effect preferably for solvent is better contacted with bonding agent, as (<2 times) not in batches, disposable solvent is all added, it is inhomogeneous that material will be mixed, and the some places solid content is higher and the some places solid content is lower; As number of times in batches too much (>4 times), prolonged the production cycle.Preferably divide 3 batches of addings, and when adding solvent, adopt blender to stir.The used blender of lithium electricity industry pulp preparation all has the function of rotation and revolution at present, it can produce a kind of with this rotation as the axle center of blender, be called " rotation ", another kind is that the blender of rotation is the rotation in axle center with the reactor center line, be called " revolution ", two kinds of motions coincide mutually, make the motion of the interior existing vertical direction of still of fluid, the motion of horizontal direction is arranged again, strong convection current spreads all over each corner of reactor, thereby make the two-phase that differs greatly mix, effect is splendid.
First solvent mainly has been wetting action, and addition is 8%~12% of a solvent total amount, and addition very few (<8%) does not have wetting effect; Addition is (>12%) too much, influences the addition of following batch of solvent.Blender revolution frequency should be adjusted to: 8~15Hz, and when stirring frequency<8Hz, rotating speed is too slow, influences wetting effect; When stirring frequency>15Hz, solvent is less because material is more, thus stirring frequency higher be easily material to be kicked up not have wetting effect.Mixing time long (>2 hours) influences production cycle of slurry; Mixing time too short (<0.5 hour) can not make material wetting fully.
Second batch of solvent mainly has been peptizaiton, and positive electrode active materials and conductive agent and bonding agent are better disperseed, and addition is 50%~65% of a solvent total amount, and solvent adding amount very few (<50%) can not make each component in the material well disperse; Addition is (>65%) too much, and the addition with the following batch solvent of influence causes the bad adjusting of viscosity of slurry.Blender revolution frequency should be adjusted to: 15~30Hz, underfrequency (<15Hz), mixing speed is slow excessively, positive electrode active materials, conductive agent and bonding agent well can not be stirred; After reaching certain stirring frequency, each component has been disperseed finely, there is no need to make frequency transfer too highly (>30Hz).Mixing time long (>1.5 hours) influences production cycle of slurry; Mixing time too short (<0.5 hour) can not make material be uniformly dispersed fully.
The effect of the 3rd batch of solvent mainly is the viscosity of regulating slurry, requires the uniformity of mixing higher, so increased the rotation of blender.The blender rotation can make slurry better disperse, and mixing time too short (<3 hours) slurry does not mix fully, and viscosity does not reach requirement; Mixing time long (>5 hours) has prolonged the production cycle, and mixes fully when stirring a period of time disposed slurry, stirs to there is no need again.
Below, by specific embodiment in detail realization of the present invention and effect are described in detail.
Embodiment 1
The auspicious Xiang 757 lithium cobalts of getting 10 long g mix with conductive agent, binding agent, auspicious Xiang lithium cobalt: conductive agent: binding agent=100: 2.5: 3.5 (mass ratio), the material that will mix carries out ball milling again, and the ball milling frequency is 30Hz, ratio of grinding media to material is 1: 1.5,1.5 hours ball milling time.The material that mill is good is poured in the mixer, solvent N-methyl pyrrolidone (NMP) adds at twice, at first add 2.1 kilograms, the blender revolution speed is 10Hz, stir and add 1.23 kilograms of solvents after 1.5 hours then, the blender revolution speed is 35Hz, and rotational velocity is 35Hz, and mixing time is 6 hours.Recording its average viscosity is 4203mPa.s, and sedimentation records its average viscosity after 24 hours be 6567mPa.s, front and back difference 2363mPa.s.
Embodiment 2
The auspicious Xiang 757 lithium cobalts of getting 10Kg mix with conductive agent, binding agent, auspicious Xiang lithium cobalt: conductive agent: binding agent=100: 2.5: 3.5 (mass ratio), and the material that will mix carries out ball milling again, and the ball milling frequency is 70Hz, and ratio of grinding media to material is 1: 2,4 hours ball milling time.The material that mill is good is poured in the mixer, solvent NMP divides four addings, at first add 0.5 kilogram, the blender revolution speed is 10Hz, stirs to add 2 kilograms of solvents after 1 hour, the blender revolution speed is 35Hz, mixing time is 1.5 hours, adds 0.5 kilogram of solvent then, and the blender revolution speed is 35Hz, rotational velocity is 38Hz, stirs after 3 hours solubilizer and continues for 0.5 kilogram to stir 1.5 hours.Recording its average viscosity is 3520mPa.s, and sedimentation records its average viscosity after 24 hours be 4800mPa.s, front and back difference 1280mPa.s.
Embodiment 3
The auspicious Xiang 757 lithium cobalts of getting 10Kg mix with conductive agent, binding agent, auspicious Xiang lithium cobalt: conductive agent: binding agent=100: 2.5: 3.5 (mass ratio), the material that will mix carries out ball milling again, and the ball milling frequency is 50Hz, ratio of grinding media to material is 1: 1.8,2 hours ball milling time.The material that mill is good is poured in the mixer, solvent NMP divides three addings, at first add 0.28 kilogram, the blender revolution speed is 8Hz, stirs to add 1.75 kilograms of solvents after 1 hour, the blender revolution speed is 20Hz, mixing time is 1 hour, adds 1.47 kilograms of solvents then, and the blender revolution speed is 35Hz, rotational velocity is 38Hz, stirs 4 hours.Recording its average viscosity is 3490mPa.s, and sedimentation records its average viscosity after 24 hours be 4703mPa.s, front and back difference 1213mPa.s.
Embodiment 4
Present embodiment preparation method and embodiment 3 are basic identical, difference is that the addition of solvent is 0.28 kilogram for the first time, the blender revolution speed is 15Hz, and mixing time is 1.5 hours, and the addition of solvent is 1.75 kilograms for the second time, the blender revolution speed is 25Hz, mixing time is 1 hour, and the addition of solvent is 1.47 kilograms for the third time, and the blender revolution speed is 35Hz, rotational velocity is 40Hz, and mixing time is 3 hours.Recording its average viscosity is 3960mPa.s, and sedimentation records its average viscosity after 24 hours be 5010mPa.s, front and back difference 1050mPa.s.
Embodiment 5
Present embodiment preparation method and embodiment 3 are basic identical, difference is that the addition of solvent is 0.3 kilogram for the first time, the blender revolution speed is 10Hz, and mixing time is 2 hours, and the addition of solvent is 2.15 kilograms for the second time, the blender revolution speed is 30Hz, mixing time is 0.5 hour, and the addition of solvent is 0.89 kilogram for the third time, and the blender revolution speed is 35Hz, rotational velocity is 38Hz, and mixing time is 4 hours.Recording its average viscosity is 4550mPa.s, and sedimentation records its average viscosity after 24 hours be 6477mPa.s, front and back difference 1927mPa.s.
Embodiment 6
Present embodiment preparation method and embodiment 3 are basic identical, difference is that the addition of solvent is 0.28 kilogram for the first time, the blender revolution speed is 8Hz, and mixing time is 1.5 hours, and the addition of solvent is 1.75 kilograms for the second time, the blender revolution speed is 25Hz, mixing time is 1.5 hours, and the addition of solvent is 1.42 kilograms for the third time, and the blender revolution speed is 40Hz, rotational velocity is 38Hz, and mixing time is 5 hours.Recording its average viscosity is 3350mPa.s, and sedimentation records its average viscosity after 24 hours be 4780mPa.s, front and back difference 1430mPa.s.
Embodiment 7
Present embodiment preparation method and embodiment 3 are basic identical, difference is that the addition of solvent is 0.28 kilogram for the first time, the blender revolution speed is 10Hz, and mixing time is 1.5 hours, and the addition of solvent is 1.92 kilograms for the second time, the blender revolution speed is 25Hz, mixing time is 0.5 hour, and the addition of solvent is 1.12 kilograms for the third time, and the blender revolution speed is 40Hz, rotational velocity is 38Hz, and mixing time is 3 hours.Recording its average viscosity is 4903mPa.s, and sedimentation records its average viscosity after 24 hours be 6490mPa.s, front and back difference 1587mPa.s.
Embodiment 8
Present embodiment preparation method and embodiment 3 are basic identical, difference is that the addition of solvent is 0.35 kilogram for the first time, the blender revolution speed is 8Hz, and mixing time is 1.5 hours, and the addition of solvent is 1.92 kilograms for the second time, the blender revolution speed is 15Hz, mixing time is 1 hour, and the addition of solvent is 1.23 kilograms for the third time, and the blender revolution speed is 35Hz, rotational velocity is 38Hz, and mixing time is 4 hours.Recording its average viscosity is 3717mPa.s, and sedimentation records its average viscosity after 24 hours be 4000mPa.s, front and back difference 283mPa.s.
Embodiment 9
Present embodiment preparation method and embodiment 3 are basic identical, difference is that the addition of solvent is 0.42 kilogram for the first time, the blender revolution speed is 10Hz, and mixing time is 1 hour, and the addition of solvent is 1.75 kilograms for the second time, the blender revolution speed is 15Hz, mixing time is 0.5 hour, and the addition of solvent is 1.28 kilograms for the third time, and the blender revolution speed is 40Hz, rotational velocity is 38Hz, and mixing time is 5 hours.Recording its average viscosity is 3657mPa.s, and sedimentation records its average viscosity after 24 hours be 4333mPa.s, front and back difference 677mPa.s.
Embodiment 10
Present embodiment preparation method and embodiment 3 are basic identical, difference is that the addition of solvent is 0.35 kilogram for the first time, the blender revolution speed is 10Hz, and mixing time is 0.5 hour, and the addition of solvent is 2.1 kilograms for the second time, the blender revolution speed is 20Hz, mixing time is 0.667 hour, and the addition of solvent is 1.00 kilograms for the third time, and the blender revolution speed is 34Hz, rotational velocity is 38Hz, and mixing time is 4 hours.Recording its average viscosity is 3257mPa.s, and sedimentation records its average viscosity after 24 hours be 3960mPa.s, front and back difference 703mPa.s.
By the foregoing description as can be seen, the anode sizing agent that adopts the inventive method to make has good homogeneous, and the viscosity difference of sedimentation after 24 hours is lower than 1000Pa.s mostly, the highest 2500Pa.s that also is no more than.

Claims (7)

1, a kind of lithium ion battery anode glue size preparation method comprises the steps:
1) with the anodal mixing of materials of weighing;
2) in mixed anodal material, add solvent and stir and make anode sizing agent; It is characterized in that: in described step 2) in solvent divide three addings;
Solvent adding amount is 8%~12% of a solvent total amount for the first time, and addition is 50%~65% of a total amount for the second time, adds remaining solvent for the third time;
Use blender to stir in the process that adds solvent, blender revolution frequency was 8~15Hz after solvent added for the first time, and mixing time is 0.5~2 hour; Blender revolution frequency was 15~30Hz after solvent added for the second time, and mixing time is 0.5~1.5 hour; Blender revolution frequency was 35~40Hz after solvent added for the third time, and rotation frequency is 35~40Hz, and mixing time is 3~5 hours.
2, lithium ion battery anode glue size preparation method according to claim 1 is characterized in that: described anodal material comprises positive electrode active materials, conductive agent and bonding agent.
3, lithium ion battery anode glue size preparation method according to claim 2 is characterized in that: adopt to grind the mixing that machinery carries out anodal material in described step 1), make anodal material levigate and mix.
4, lithium ion battery anode glue size preparation method according to claim 3 is characterized in that: the described machinery that grinds is ball mill.
5, lithium ion battery anode glue size preparation method according to claim 4 is characterized in that: the technological parameter of described ball mill in the mixing of materials process is ball milling frequency 30~70Hz, ratio of grinding media to material 1: 2~1: 1.5, milling time 1.5~4 hours.
6, a kind of positive plate that in the anode sizing agent preparation process, has used the lithium ion battery of the described method of above-mentioned any one claim.
7, a kind of lithium ion battery with the described positive plate of claim 6.
CNB2005100205587A 2005-03-17 2005-03-17 Lithium ion battery anode glue size preparation method, positive plate and lithium ion battery Expired - Fee Related CN100547828C (en)

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CN100547828C true CN100547828C (en) 2009-10-07

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CN102088076A (en) * 2010-12-25 2011-06-08 东莞市良源电池科技有限公司 Preparation method of anode of lithium ion battery
CN102810663A (en) * 2011-06-02 2012-12-05 珠海银通新能源有限公司 Preparation method of lithium ion battery slurry, battery pole piece and lithium ion battery
CN103280566B (en) * 2013-05-31 2015-07-08 广东凯德能源科技有限公司 Preparation methods of positive and negative pole pastes for lithium ion batteries
CN104766949B (en) * 2014-01-08 2017-05-03 中山天贸电池有限公司 Processing method of lithium ion battery negative electrode slurry
CN104466090B (en) * 2014-12-16 2018-04-06 江苏华东锂电技术研究院有限公司 Cell size preparation method
CN104577071B (en) * 2015-01-28 2016-12-07 山东齐星新能源科技有限责任公司 A kind of lithium ion battery dry powder pulping process
CN105185951A (en) * 2015-08-24 2015-12-23 深圳市斯诺实业发展有限公司 Preparation method of lithium battery cathode slurry
CN105161676A (en) * 2015-08-25 2015-12-16 田东 Preparation method for lithium iron phosphate cathode slurry
CN106410141A (en) * 2016-10-19 2017-02-15 江苏海四达电源股份有限公司 Cylindrical lithium ion battery for electric tool and preparation method of cylindrical lithium ion battery
CN106654153A (en) * 2016-12-16 2017-05-10 东莞市创明电池技术有限公司 Slurry for lithium-ion battery and slurry synthesizing method
CN109256523A (en) * 2018-09-15 2019-01-22 珠海光宇电池有限公司 A kind of preparation method for the lithium ion battery improving high-voltage anode material comprehensive performance
CN110459738A (en) * 2019-06-24 2019-11-15 东莞维科电池有限公司 Lithium ion battery anode glue size and preparation method thereof, positive plate, lithium ion battery
CN112952090B (en) * 2021-01-26 2023-02-07 惠州亿纬锂能股份有限公司 Preparation method of lithium battery positive electrode slurry and lithium battery positive electrode slurry prepared by same
CN114725310A (en) * 2022-04-11 2022-07-08 湖南钠方新能源科技有限责任公司 Positive electrode slurry and preparation method thereof, positive plate and secondary battery
CN115050949B (en) * 2022-08-11 2022-11-04 楚能新能源股份有限公司 Positive electrode slurry, preparation method thereof and lithium ion battery

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