CN112563483A - Positive active material slurry of lithium ion battery and preparation method - Google Patents

Positive active material slurry of lithium ion battery and preparation method Download PDF

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Publication number
CN112563483A
CN112563483A CN202011468802.7A CN202011468802A CN112563483A CN 112563483 A CN112563483 A CN 112563483A CN 202011468802 A CN202011468802 A CN 202011468802A CN 112563483 A CN112563483 A CN 112563483A
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slurry
active material
lithium ion
ion battery
binder
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刘国壮
黄斌
黄光炜
黄定东
许欣凡
李沅蓉
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Guangxi Zhuoneng New Energy Science & Technology Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/021Physical characteristics, e.g. porosity, surface area
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A preparation method of positive active material slurry of a lithium ion battery comprises the following steps: s1: weighing the active matter, the binder, the conductive agent and the deionized water according to the amount, adding the active matter, the binder, the conductive agent and the deionized water into a double-planet pulping machine together, and stirring for 1.5-3h under the conditions that the revolution speed is 48 revolutions per minute and the autodrive speed is 1700 revolutions per minute to prepare slurry, so that the viscosity of the slurry without mixing reaches 3000-15000 mPa.s; s2: and (4) dispersing the slurry obtained in the step S1 by using a high-speed dispersion machine under the condition that the rotating speed is 3000-6000 r/min until the viscosity reaches 3000-15000 mPa.s, thus obtaining the active material slurry of the positive electrode of the lithium ion battery. The slurry prepared by the preparation method of the lithium ion battery anode active material slurry still has the advantages of high stability and good fluidity in a high-humidity environment.

Description

Positive active material slurry of lithium ion battery and preparation method
[ technical field ] A method for producing a semiconductor device
The invention relates to anode active material slurry of a lithium ion battery, in particular to anode active material slurry of the lithium ion battery and a preparation method thereof.
[ background of the invention ]
With the development of mobile electronic devices, batteries are increasingly demanded, and therefore, higher requirements are made on the capacity, voltage, service life and use cost of the batteries. A lithium ion battery is a type of secondary battery (i.e., a rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. However, the lithium ion batteries on the market have various defects of poor cell safety performance, low capacity per unit volume, low power and poor cycle performance, and the defects are caused by the unqualified viscosity of slurry for manufacturing the positive plate. Secondly, the pulping processing performance of the anode active matter of the existing lithium ion battery is unstable; particularly, the oiliness process nmp (low toxicity and flammability) of nickel cobalt lithium manganate is used as a solvent, PVDF is used as a binder, the requirement on the humidity of the production environment is high after the slurry is prepared, because the PVDF is agglomerated and fails after absorbing water, the slurry is easy to thicken and weaken in fluidity under a high humidity environment (more than or equal to 10% RH), the coating surface density is unstable, the adhesion of pole piece powder is worsened, and various problems are caused, such as the qualification rate of the produced product is lower than 90%, the consistency is poor, the comprehensive performance of the product is worsened, the cycle performance is unstable, and the low temperature and rate performance are worsened. Therefore, there is a high necessity for a slurry having a viscosity and a fluidity that satisfy the use requirements even in a high-humidity environment.
[ summary of the invention ]
In order to solve the problems, the invention provides the positive electrode active material slurry of the lithium ion battery and the preparation method thereof, and the slurry prepared by the method still has the advantages of high stability and good fluidity under a high-humidity environment.
The invention is realized by the following technical scheme, and provides a preparation method of anode active material slurry of a lithium ion battery, which comprises the following steps:
s1: weighing the active matter, the binder, the conductive agent and the deionized water according to the amount, adding the active matter, the binder, the conductive agent and the deionized water into a double-planet pulping machine together, and stirring for 1.5-3h under the conditions that the revolution speed is 48 revolutions per minute and the autodrive speed is 1700 revolutions per minute to prepare slurry, so that the viscosity of the slurry without mixing reaches 3000-15000 mPa.s;
s2: and (4) dispersing the slurry obtained in the step S1 by using a high-speed dispersion machine under the condition that the rotating speed is 3000-6000 r/min until the viscosity reaches 3000-15000 mPa.s, thus obtaining the active material slurry of the positive electrode of the lithium ion battery.
Specifically, in the step S1, the active material, the binder, and the conductive agent are calculated by weight percentage, and the specific contents are as follows:
93-97.5% of active matter;
1.5 to 3 percent of binder;
1-4% of a conductive agent;
the active matter is lithium nickel manganese oxide, the binder is a composition of any two of CMC, SBR, PAA, sodium alginate and chitosan and PAA, and the conductive agent is a composition of any two of conductive carbon black, crystalline flake graphite and graphene; in the invention, the binder is made of hydrophilic materials, wherein the hydrophilic materials have a suspension effect, SBR and chitosan account for 0-1% to have a bonding effect, the rest part is PAA to have a reinforced bonding effect, CMC has a bonding effect between powder materials and suspension SBR has a bonding effect between powder materials and a fluid collection body, PAA has a bonding effect between powder materials and the fluid collection body, sodium alginate has a bonding effect and a suspension effect between powder materials, and chitosan has a bonding effect between the powder materials and the fluid collection body; the conductive carbon black plays a role in the electric conduction between active matters and with a current collector; the crystalline flake graphite plays a role in improving the particle compaction of the active matters while playing a role in conducting electricity between the active matters and the current collector; the graphene has the same conductive capacity between active matters and as a current collector under the condition that the addition amount of the graphene is 80% less than that of conductive carbon black, the compaction density of active matter particles can be improved, the energy density of a battery is improved, the low specific energy of the battery is combined, the liquid injection time is short in the manufacturing process of the battery, and the yield is effectively improved by over 50%.
Specifically, the mixture of the active material, the binder, the conductive agent and the deionized water in the step S1 is (7-7.8): (2.2-3) mixing is performed so that the slurry can achieve the viscosity required for coating.
The lithium ion battery anode active material slurry prepared by the preparation method of the lithium ion battery anode active material slurry is used for finally preparing a battery with excellent performance.
In the invention, deionized water is adopted to replace NMP (which is low in toxicity and inflammable) adopted in the prior art as a solvent to prepare slurry, the process is environment-friendly and safe, and a novel conductive agent is added for composite use, so that the energy density of the battery is improved, the combined cost is low, the specific energy is high, and the liquid injection time in the battery manufacturing process is short, and the yield is effectively improved by more than 50%.
Finally, coating the prepared slurry on an aluminum foil with the thickness of 12-16 mu m according to the surface density of 200-230 g/square meter, and drying to prepare a positive plate; can also be 3.4-3.6 g/mm according to the active matter3The compacted density is rolled to prepare the compacted positive plate.
The invention provides a lithium ion battery anode active substance slurry, which is prepared from an active substance (nickel lithium manganate), a binder (CMC \ SBR \ PAA \ sodium alginate \ chitosan), a conductive agent (conductive carbon black, flake graphite, graphene) and a solvent (deionized water), wherein an oil-based PVDF binder is replaced by a water-based binder (CMC \ SBR \ PAA \ sodium alginate \ chitosan and the like), so that the material cost is reduced, the preparation is more environment-friendly and safe, the conductive agent (conductive carbon black, flake graphite, graphene and the like) conforms to the use of various materials, the conductive compaction and the energy density of a pole piece can be better improved, a battery with high energy, low cost and safety can be prepared by using the active substance (nickel lithium manganate), and the solvent deionized water is environment-friendly and has low cost. In conclusion, the slurry prepared by the materials has good stability, no combustible components, no toxic and harmful substances, low cost and good processability of the prepared battery cell, can effectively improve the liquid injection speed by more than 50 percent and shorten the production period by more than 3 days; the lithium ion battery produced by the positive plate prepared by the slurry is not easy to cause short circuit of the battery, and has the advantages of long service life, good low-temperature charge and discharge performance, high energy density, safe use, stable cycle performance and the like, and the cost performance of the conventional battery is lower by more than 10%.
[ description of the drawings ]
Fig. 1 is a schematic diagram of capacity retention rate of a lithium ion battery finally prepared by using the lithium ion battery anode active material slurry of the invention at cycle performance of 800 times.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail by the following embodiments.
Example 1:
a lithium ion battery positive active material slurry comprising the components:
Figure BDA0002835418890000041
s1: weighing the components according to the mass percent, weighing a certain amount of deionized water to obtain a mixed solution, wherein the solid content of the mixed solution is 73-78%, adding the mixed solution into a double-planet pulping machine, and stirring for 2 hours under the conditions that the revolution speed is 48 revolutions per minute and the autokinetic transfer speed is 1700 revolutions per minute to prepare slurry;
s2: dispersing the slurry obtained in the step S1 by adopting a high-speed dispersion machine under the condition that the rotating speed is 3500 rpm/min until the viscosity reaches 5000mPa.s, thus obtaining the active material slurry of the positive electrode of the lithium ion battery
Example 2:
a lithium ion battery positive active material slurry comprising the components:
Figure BDA0002835418890000042
s1: weighing the components according to the mass percentage, weighing a certain amount of deionized water to obtain a mixed solution, wherein the solid content of the mixed solution is 70-76%, adding the mixed solution into a double-planet pulping machine, and stirring for 2.5 hours under the conditions that the revolution speed is 48 revolutions per minute and the autokinetic transfer speed is 1500 revolutions per minute to prepare slurry;
s2: and (4) dispersing the slurry obtained in the step S1 by using a high-speed dispersion machine under the condition that the rotating speed is 4000 revolutions per minute until the viscosity reaches 10000mPa.s, thus obtaining the lithium ion battery anode active material slurry.
Example 3:
a lithium ion battery positive active material slurry comprising the components:
Figure BDA0002835418890000051
s1: weighing the components according to the mass percent, then weighing a certain amount of deionized water to obtain a mixed solution, wherein the solid content of the mixed solution is 70-76%, adding the mixed solution into a double-planet pulping machine, and stirring for 2.5 hours under the conditions that the revolution speed is 48 revolutions per minute and the autokinetic transfer speed is 1800 revolutions per minute to prepare slurry;
s2: and (4) dispersing the slurry obtained in the step S1 by using a high-speed dispersion machine at the rotating speed of 6000 r/min until the viscosity reaches 10000mPa.s, thus obtaining the lithium ion battery anode active material slurry.
The positive electrode slurry provided by the embodiments 1 to 3 has good surface density consistency of the manufactured positive electrode plate, has high liquid injection speed, and can complete liquid injection only in 6 minutes, while the prior art can meet the requirement only in 13 minutes of liquid injection, so that the slurry provided by the invention has good fluidity in a high-humidity environment, thereby greatly shortening the liquid injection time, and being capable of manufacturing a lithium battery with better quality, meanwhile, the slurry provided by the invention has short activation and aging time of only 36 hours, and the prior art needs 48 hours, and further, the processing time can be saved while the quality of the lithium battery is improved, therefore, the slurry provided by the invention can greatly shorten the production period and improve the processing efficiency while improving the liquid injection speed.
In order to prove that the performance of the lithium battery manufactured by the slurry provided by the invention is improved compared with the lithium battery manufactured by the prior art, the lithium batteries produced by the above embodiment and the prior art are detected by the following steps of detecting the security inspection passing rate, the cycle performance and the discharge platform, and the obtained detection results are shown in table 1 and fig. 1.
TABLE 1
Figure BDA0002835418890000061
As can be seen from table 1 in conjunction with fig. 1, the lithium batteries prepared by the embodiments of the present invention are superior to the prior art compared to the prior art comparative examples; the battery core manufactured by the embodiment of the invention passes 100% of safety test of a power storage battery for an electric automobile according to GBT31485-2015 safety requirement and a test method, the cycle performance is excellent (800 weeks), and the discharge platform is 3.7V, while the cycle performance of the battery core manufactured by the comparative example is greatly reduced compared with the cycle performance of the battery core manufactured by the embodiment of 800 weeks after only 500 weeks of cycle performance, so that the cycle performance of the lithium battery prepared by the slurry provided by the invention is greatly improved, and the lithium battery prepared by the slurry has the advantages of long service life, good low-temperature charge and discharge performance, high energy density, safety in use, stable cycle performance and the like.

Claims (4)

1. The preparation method of the positive active material slurry of the lithium ion battery is characterized by comprising the following steps of:
s1: weighing the active matter, the binder, the conductive agent and the deionized water according to the amount, adding the active matter, the binder, the conductive agent and the deionized water into a double-planet pulping machine together, and stirring for 1.5-3h under the conditions that the revolution speed is 48 revolutions per minute and the autodrive speed is 1700 revolutions per minute to prepare slurry, so that the viscosity of the slurry without mixing reaches 3000-15000 mPa.s;
s2: and (4) dispersing the slurry obtained in the step S1 by using a high-speed dispersion machine under the condition that the rotating speed is 3000-6000 r/min until the viscosity reaches 3000-15000 mPa.s, thus obtaining the active material slurry of the positive electrode of the lithium ion battery.
2. The method for preparing the slurry of the positive electrode active material of the lithium ion battery according to claim 1, wherein the active material, the binder and the conductive agent in the step S1 comprise the following components in percentage by weight:
93-97.5% of active matter; the processing is not good and the specific energy is low
1.5 to 3 percent of binder;
1-4% of a conductive agent;
the active matter is lithium nickel manganese oxide, the binder is a composition of any two of CMC, SBR, PAA, sodium alginate and chitosan and PAA, the CMC and sodium alginate account for 0-1% of the composition and play a role in suspension, the SBR and chitosan account for 0-1% of the composition and play a role in adhesion, the rest of the composition is PAA and plays a role in reinforcing adhesion, and the conductive agent is a composition of any two of conductive carbon black, flake graphite and graphene.
3. The method for preparing the lithium ion battery positive electrode active material slurry according to claim 2, wherein the mixture of the active material, the binder, the conductive agent and the deionized water in the step S1 is prepared according to the following steps of (7-7.8): (2.2-3) mixing.
4. A lithium ion battery positive electrode active material slurry prepared according to the preparation method of the lithium ion battery positive electrode active material slurry of any one of claims 1 to 3.
CN202011468802.7A 2020-12-14 2020-12-14 Positive active material slurry of lithium ion battery and preparation method Pending CN112563483A (en)

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Cited By (2)

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CN114614007A (en) * 2022-02-17 2022-06-10 东莞凯德新能源有限公司 Lithium ion battery anode slurry and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN114068915A (en) * 2021-11-04 2022-02-18 惠州锂威新能源科技有限公司 Preparation method and application of positive electrode slurry
CN114614007A (en) * 2022-02-17 2022-06-10 东莞凯德新能源有限公司 Lithium ion battery anode slurry and preparation method thereof

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Application publication date: 20210326