CN111525133A - Composite conductive agent, lithium ion positive electrode material prepared from composite conductive agent and lithium ion battery - Google Patents

Composite conductive agent, lithium ion positive electrode material prepared from composite conductive agent and lithium ion battery Download PDF

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Publication number
CN111525133A
CN111525133A CN202010219218.1A CN202010219218A CN111525133A CN 111525133 A CN111525133 A CN 111525133A CN 202010219218 A CN202010219218 A CN 202010219218A CN 111525133 A CN111525133 A CN 111525133A
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conductive agent
lithium ion
composite conductive
positive electrode
composite
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赵顶
赵林
赵澎
但勇
陈雪风
何永
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Meishan Shunying Power Battery Material Co ltd
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Meishan Shunying Power Battery Material Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a composite conductive agent and a lithium ion anode material and a lithium ion battery prepared from the same, wherein the composite conductive agent mainly comprises a conductive agent A and a conductive agent B; the conductive agent A is one or two of acetylene black and conductive graphite; the conductive agent B is TinO2n‑1Wherein 3 is titanium oxide of<n<10; the conductive agent B is titanium oxide or a mixture of a plurality of titanium oxides; the mass of the conductive agent B accounts for 1-50% of that of the composite conductive agent. According to the invention, on the basis of common conductive agents of acetylene black and conductive graphite, titanium suboxide is added, the prepared composite conductive agent is used for preparing the anode material of the lithium ion battery, and the discharge capacity, the rate capability and the charge-discharge cycle performance of the lithium ion battery prepared by the composite conductive agent are remarkably improved.

Description

Composite conductive agent, lithium ion positive electrode material prepared from composite conductive agent and lithium ion battery
Technical Field
The invention belongs to the technical field of lithium battery preparation, and particularly relates to a composite conductive agent, a lithium ion anode material prepared from the composite conductive agent, and a lithium ion battery.
Background
With the aggravation of energy crisis and environmental pollution, new energy Electric Vehicles (EV) have been developed very rapidly, and lithium ion batteries have been widely used in the field of electric vehicles.
The anode material is the core of the power lithium ion battery, the energy density of the anode material is closely related to the driving mileage of the electric automobile, and the cost of the anode material accounts for about one third of the cost of the lithium battery. The positive electrode material is a semiconductor even an insulator with poor conductivity, and the conductivity needs to be enhanced by adding the conductive agent, so that the charge transfer capacity is enhanced, the internal resistance of the battery is reduced, the excellent performance of the positive electrode active material cannot be exerted without adding the conductive agent, and the conductive agent as an important component of the lithium ion battery plays an important role in improving the discharge capacity, rate capability and cycle performance of the battery.
The conventional conductive agents are acetylene black and conductive carbon black, but the acetylene black is granular, the specific surface area of the conductive carbon black is large, the conductive carbon black is poor in dispersibility in slurry, easy to agglomerate, and has strong oil absorption, so that the conductive network is not easily formed, the polarization of an electrode is serious, and the utilization rate of an active material and the energy density of a battery are still limited.
Disclosure of Invention
The invention aims to: the invention provides a composite conductive agent and a lithium ion positive electrode material and a lithium ion battery prepared from the composite conductive agent, aiming at the technical problem that the conductive agent in the lithium ion battery in the prior art has limited capability of improving the utilization rate of the positive electrode active material and the performance of the battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a composite conductive agent mainly comprises a conductive agent A and a conductive agent B;
the conductive agent A is one or two of acetylene black and conductive graphite;
the conductive agent B is TinO2n-1Wherein 3 is titanium oxide of<n<10；
The conductive agent B is titanium oxide or a mixture of a plurality of titanium oxides;
the mass of the conductive agent B accounts for 1-50% of that of the composite conductive agent.
The invention adds titanium dioxide on the basis of common conductive agents of acetylene black and conductive graphite, the prepared composite conductive agent is used for preparing the anode material of the lithium ion battery, the discharge capacity, the rate capability and the charge-discharge cycle performance of the lithium ion battery prepared by the composite conductive agent are obviously improved, and the titanium element in the titanium dioxide mainly adopts Ti3+、Ti4+Is present of Ti3+The introduction of the lithium ion conductive polymer can effectively improve the migration efficiency of lithium ions in the lithium ion battery, shorten the diffusion path of the lithium ions, obviously improve the performance of the battery, and have good acid-base tolerance and stability.
Further, the conductive agent B is Ti4O7、Ti5O9、Ti6O11、Ti7O13、Ti8O15、Ti9O17One or more of them.
Further, the mass of the conductive agent B accounts for 1-20% of the composite conductive agent. Researches find that the performance of the assembled lithium ion battery is better when the conductive agent B accounts for 1-20% of the composite conductive agent by mass. For example, the mass ratio of the conductive agent B may be 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.5%, 3.0%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 7%, 10%, 12%, 15%, 18%, or the like.
Further, the particle size of the conductive agent B is 1 nm-3 μm. Preferably, the particle size of the conductive agent B is 500nm to 3 μm. The particle size is too large, so that a conductive network is not easily formed, and the polarization of the electrode is serious.
Further, the specific surface area of the conductive agent B is 1-20 m2g-1Preferably, the specific surface area of the conductive agent B is 5-10 m2g-1. The smaller the particle size of the material is, the larger the total specific surface area is, the larger the specific surface area of the conductive agent is, the more favorable the contact between the conductive agent and the electrolyte is, and the better the battery performance is. However, the specific surface area is too large, the surface energy of the product is increased, the material is agglomerated, the dispersion is not facilitated, and the comprehensive performance of the battery is reduced.
Further, the production method of titanium suboxide is generally a reduction method and an oxidation method. The main method is a reduction method, wherein the reduction method generally takes titanium dioxide as a raw material and is prepared by reduction at high temperature, and the used reducing agents comprise hydrogen, carbon and active metals such as sodium, magnesium, titanium and the like. Such as: the titanium dioxide can be prepared into Ti phase at 1100 ℃ for two hours in hydrogen atmosphere4O7Titanium (ii) oxide.
The preparation method of the composite conductive agent mainly comprises the following steps: and mixing the conductive agent A and the conductive agent B according to the proportion, and uniformly stirring to obtain the composite conductive agent.
The preparation method is simple, efficient and easy to realize industrialization.
The invention also provides a positive electrode material prepared by adopting the composite conductive agent.
The discharge capacity, rate capability and charge-discharge cycle performance of the lithium ion battery prepared by the composite conductive agent are obviously improved, and the titanium element in the titanium suboxide mainly adopts Ti3+、Ti4+Is present of Ti3+The introduction of the lithium ion conductive polymer can effectively improve the migration efficiency of lithium ions in the lithium ion battery, shorten the diffusion path of the lithium ions, obviously improve the performance of the battery, and have good acid-base tolerance and stability.
Further, the positive electrode material comprises a positive electrode active material, a composite conductive agent and a binder.
Further, the preparation method of the cathode material comprises the following steps: and mixing the composite conductive agent, the positive active substance and the adhesive in proportion, and stirring to obtain slurry serving as a positive material.
Further, the positive electrode active material is LiNi1-x-yCoxMnyO2Wherein 0 is<x≤0.34，0<y is less than or equal to 0.34. Preferably, the positive electrode active material is LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.3O2、LiNi1/3Co1/3Mn1/3O2、LiNi0.8Co0.15Al0.05O2、LiNi0.6Co0.2Al0.2O2One or more of (a).
Further, the composite conductive agent accounts for 8-10% of the total mass of the lithium ion positive electrode material.
Further, the adhesive is one or more of polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR) emulsion and carboxymethyl cellulose (CMC).
The invention also provides a positive electrode of the lithium ion battery, which comprises a current collector and a positive electrode material coated and/or filled on the current collector, wherein the positive electrode material is prepared by adding and applying the composite conductive agent.
Further, the composite conductive agent, the positive active material and the adhesive are mixed to prepare slurry, and the slurry is coated, dried and cut to obtain the positive electrode.
The invention also provides a lithium ion battery which is assembled by the anode.
Through the positive electrode active material, TinO2n-1Simple mixing of powder, acetylene black and binder to realize TinO2n-1The method is simple, efficient and easy to realize industrialization, and the performance can be obviously improved.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, on the basis of common conductive agents of acetylene black and conductive graphite, titanium suboxide is added, the prepared composite conductive agent is used for preparing the anode material of the lithium ion battery, and the discharge capacity, the rate capability and the charge-discharge cycle performance of the lithium ion battery prepared by the composite conductive agent are remarkably improved.
2. The preparation method of the composite conductive agent is simple, the performance of the prepared lithium ion battery is high, and industrialization is easy to realize.
Drawings
FIG. 1 shows the results of the rate capability tests of the lithium ion batteries prepared in examples 1 to 5 of the present invention and comparative example 1.
FIG. 2 shows the results of cycle performance tests of lithium ion batteries prepared in examples 1 to 5 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation process of the lithium ion battery comprises the following steps: (1) mixing TinO2n-1Mixing with acetylene black and/or conductive carbon black in a certain proportion to be used as a composite conductive agent;
(2) and mixing the composite conductive agent, the positive active substance and the adhesive to prepare slurry, and then coating, drying and cutting to obtain the positive electrode. And then injecting electrolyte into the anode, the diaphragm and the cathode material (graphite cathode) to assemble the lithium ion battery for subsequent performance test.
Example 1
The positive electrode contained 80 wt% of an active material (LiNi)0.8Co0.1Mn0.1O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (0.2 wt% of Ti)nO2n-1Powder and 9.8 wt% of acetylene black), Ti in the conductive agentnO2n-1The powder is Ti4O7、Ti5O9、Ti6O11Mixture of (A) and (B), TinO2n-1The conductive agent is in the form of particles with a particle size of about 1 μm and a specific surface area of 2.7m2g-1. Prepared from the cathode materialThe ternary lithium ion battery is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C, respectively, and finally the obtained test results are shown in fig. 2. The discharge capacities thereof are 196.3, 189.8, 172.6, 154.3, 142.9, 127.5 and 110.1mAhg respectively-1The reversible capacity retention rate is 80.6 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 2
The positive electrode contained 80 wt% of an active material (LiNi)0.8Co0.1Mn0.1O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (0.5 wt% of Ti)nO2n-1Powder and 9.5 wt% acetylene black) in conductive agentnO2n-1The powder is Ti as main phase4O7，Ti5O9Mixture of (A) and (B), TinO2n-1The conductive agent is granular, has a particle diameter of about 1 μm and a specific surface area of 2.3m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively, and finally the obtained test result is shown in FIG. 2. The discharge capacities thereof are 204.6, 198.9, 187.2, 179.1, 174.1, 166.1 and 158.9mAhg respectively-1The reversible capacity retention rate is 85.3 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 3
The positive electrode contained 80 wt% of an active material (LiNi)0.8Co0.1Mn0.1O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (1.0 wt% of Ti)nO2n-1Powder and 9.0 wt% acetylene black) in conductive agentnO2n-1The powder is Ti as main phase4O7，Ti6O11，Ti9O17Mixture of (A) and (B), TinO2n-1The conductive agent is in the form of particlesGranular with a particle size of 800nm and a specific surface area of 2.8m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively, and finally the obtained test result is shown in FIG. 2. The discharge capacities thereof were 204.5, 199.2, 189.2, 180.1, 172.5, 161.2, 150.5mAhg, respectively-1The reversible capacity retention rate is 82.3 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 4
The positive electrode contained 80 wt% of an active material (LiNi)0.8Co0.1Mn0.1O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (2.0 wt% of Ti)nO2n-1Powder and 8.0 wt% of acetylene black) in conductive agentnO2n-1The powder is Ti as main phase4O7，Ti5O9，Ti8O15Mixture of (A) and (B), TinO2n-1The conductive agent is granular, the grain diameter is about 1.2 μm, and the specific surface area is 2.12m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively, and finally the obtained test result is shown in FIG. 2. The discharge capacities thereof are 199.3, 191.8, 180.6, 170.3, 160.9, 145.5 and 128.1mAhg respectively-1The reversible capacity retention rate is 80.4 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 5
The positive electrode contained 80 wt% of an active material (LiNi)0.8Co0.1Mn0.1O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (4 wt% of Ti)nO2n-1Powder and 6.0 wt% acetylene black) of a conductive agentnO2n-1The powder is Ti as main phase4O7，Ti5O9，Ti6O11Mixture of (A) and (B), TinO2n-1The conductive agent is granular, has a particle diameter of about 2 μm and a specific surface area of 1.5m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively, and finally the obtained test result is shown in FIG. 2. The discharge capacities thereof are 190.3, 185.3, 174.7, 165.6, 155.6, 134.5 and 96.4mAhg respectively-1The reversible capacity retention rate is 82.1 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 6
The positive electrode contained 80 wt% of an active material (LiNi)0.5Co0.2Mn0.3O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (0.5 wt% of Ti)nO2n-1Powder and 9.5 wt% acetylene black) in conductive agentnO2n-1The powder is Ti as main phase4O7，Ti5O9，Ti8O15Mixture of (A) and (B), TinO2n-1The conductive agent is granular, has a particle diameter of 500nm and a specific surface area of 10.7m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C, and has discharge capacities of 180.2, 174.5, 163.7, 155.7, 150.2, 142.0, 134.4mAhg-1The reversible capacity retention rate of the battery is 86.7 percent when 50 cycles are carried out at the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 7
The positive electrode contained 80 wt% of an active material (LiNi)0.5Co0.2Mn0.3O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (2.0 wt% of Ti)nO2n-1Mixing the powder with 8.0 wt% of BAcetylene black) conductive agentnO2n-1The powder is Ti as main phase4O7，Ti5O9，Ti8O15Mixture of (A) and (B), TinO2n-1The conductive agent is granular, has a particle diameter of 120nm and a specific surface area of 17.7m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively, and has discharge capacities of 176.1, 165.5, 154.7, 143.2, 133.7, 118.1 and 100.5mAhg respectively-1The reversible capacity retention rate of the battery is 81.2 percent when 50 cycles are carried out at the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 8
The positive electrode contained 80 wt% of an active material (LiNi)0.8Co0.15Al0.05O2) 10 wt% of a binder (SBR), 10 wt% of a conductive agent (0.5 wt% of Ti)nO2n-1Powder and 9.5 wt% of conductive carbon black) Ti in the conductive agentnO2n-1The powder is Ti as main phase4O7，Ti5O9Mixture of (A) and (B), TinO2n-1The conductive agent is granular, has a particle diameter of 300nm and a specific surface area of 12.7m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C, and has discharge capacities of 209.8, 203.9, 192.7, 184.2, 180.4, 172.6 and 164.1mAhg-1The reversible capacity retention rate of the battery is 84.9 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 9
The positive electrode contained 80 wt% of an active material (LiNi)0.8Co0.15Al0.05O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (1.0 wt% of Ti)nO2n-1Powder and 9.0 wt% acetylene black) in conductive agentnO2n-1The powder is Ti as main phase4O7Mixture of (A) and (B), TinO2n-1The conductive agent is granular, has a particle diameter of 2.4 μm and a specific surface area of 1.3m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at the charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively, and the discharge capacities of the ternary lithium ion battery are 204.4, 202.3, 190.7, 180.6, 170.2, 155.1 and 132.9mAhg respectively-1The reversible capacity retention rate is 80.1 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 10
The positive electrode contained 80 wt% of an active material (LiNi)1/3Co1/3Mn1/3O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (0.5 wt% of Ti)nO2n-1Powder and 9.5 wt% of conductive carbon black) Ti in the conductive agentnO2n-1The powder is Ti as main phase4O7，Ti5O9，Ti6O11Mixture of (A) and (B), TinO2n-1The conductive agent is granular, has a particle diameter of about 2.2 μm and a specific surface area of 1.6m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively, and has discharge capacities of 168.7, 162.5, 152.8, 144.1, 140.3, 132.4 and 124.5mAhg respectively-1The reversible capacity retention rate of the battery is 86.1 percent when 50 cycles are carried out at the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 11
The positive electrode contained 80 wt% of an active material (LiNi)1/3Co1/3Mn1/3O2) 10 wt% of a binder (PVDF), 10 wt% of a conductive agent (1.0 wt% of Ti)nO2n-1Powder and 9.0 wt% of acetylene black and conductive carbon black) as conductive agentnO2n-1The powder is Ti as main phase4O7，Ti5O9，Ti6O11Mixture of (A) and (B), TinO2n-1The conductive agent is granular, has a particle diameter of about 2 and a specific surface area of 1.8m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively, and has discharge capacities of 168.5, 163.7, 153.7, 144.7, 136.7, 125.9 and 115.9mAhg respectively-1The reversible capacity retention rate is 82.7 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Example 12
The positive electrode contained 70 wt% of an active material (LiNi)1/3Co1/3Mn1/3O2) 15 wt% of a binder (PVDF), 15 wt% of a conductive agent (2.0 wt% of Ti)nO2n-1Powder and 8.0 wt% of acetylene black) in conductive agentnO2n-1The powder is Ti as main phase4O7，Ti5O9，Ti6O11Mixture of (A) and (B), TinO2n-1The conductive agent is granular, has a particle diameter of 2.1 and a specific surface area of 1.8m2g-1. The ternary lithium ion battery prepared by the cathode material is subjected to charge-discharge cycles at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively, and has discharge capacities of 163.3, 155.3, 144.6, 135.6, 127.2, 112.7 and 93.2mAhg respectively-1The reversible capacity retention rate is 80.1 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
Comparative example 1
Comparative example 1 is different from example 1 in that all of the conductive agents used in comparative example 1 were acetylene black, and other raw materials and amounts thereof, preparation methods and amounts thereofExample 1 was identical and the performance of the assembled lithium ion battery of comparative example 1 was tested as follows: the discharge capacity of the material is respectively 194.4, 180.9, 160.4, 150.1, 138.7, 121.9 and 95.6mAhg when the material is subjected to charge-discharge circulation at the charge-discharge rate of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C-1When 50 cycles were performed at a charge/discharge rate of 0.2C, the reversible capacity retention rate was only 75.1%.
Comparative example 2
Comparative example 1 is different from example 10 in that all the conductive agents used in comparative example 1 are conductive carbon black, the preparation method is completely the same as that of example 1 for other raw materials and the use amount, and the performance test is performed on the lithium ion battery assembled in comparative example 1, and the test results are as follows: the discharge capacity of the lithium ion battery is 158.6, 144.5, 124.3, 114.1, 106.7, 87.3 and 72.5mAhg after charge-discharge circulation at the charge-discharge rate of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C respectively-1The reversible capacity retention rate is 73.2 percent when 50 cycles are carried out under the charge-discharge rate of 0.2C, and the battery is added with TinO2n-1And then the discharge capacity, rate capability and cycle performance of the material are all obviously improved.
The invention adds titanium dioxide on the basis of common conductive agents of acetylene black and conductive graphite, the prepared composite conductive agent is used for preparing the anode material of the lithium ion battery, the discharge capacity, the rate capability and the charge-discharge cycle performance of the lithium ion battery prepared by the composite conductive agent are obviously improved, and the titanium element in the titanium dioxide mainly adopts Ti3+、Ti4+Is present of Ti3+The introduction of the lithium ion conductive polymer can effectively improve the migration efficiency of lithium ions in the lithium ion battery, shorten the diffusion path of the lithium ions, obviously improve the performance of the battery, and have good acid-base tolerance and stability.
The descriptions of each patent, patent application, and publication cited in this application are incorporated herein by reference in their entirety. Citation of any reference shall not be construed as an admission that such reference is available as "prior art" to the present application.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. The composite conductive agent is characterized by mainly comprising a conductive agent A and a conductive agent B;
the conductive agent A is one or two of acetylene black and conductive graphite;
the conductive agent B is TinO2n-1Wherein 3 is titanium oxide of<n<10；
The conductive agent B is titanium oxide or a mixture of a plurality of titanium oxides;
the mass of the conductive agent B accounts for 1-50% of that of the composite conductive agent.
2. The composite conductive agent according to claim 1, wherein the conductive agent B accounts for 1 to 20% by mass of the composite conductive agent.
3. The composite conductive agent according to claim 1, wherein the conductive agent B is Ti4O7、Ti5O9、Ti6O11、Ti7O13、Ti8O15、Ti9O17One or more of them.
4. The composite conductive agent according to claim 1, wherein the particle diameter of the conductive agent B is 1nm to 3 μm.
5. The composite conductive agent according to claim 1, wherein the specific surface area of the conductive agent B is 1m2g-1～20m2g-1。
6. A method for preparing the composite conductive agent as claimed in any one of claims 1 to 5, which mainly comprises the following steps: and mixing the conductive agent A and the conductive agent B according to the proportion, and uniformly stirring to obtain the composite conductive agent.
7. A lithium ion positive electrode material prepared using the composite conductive agent according to any one of claims 1 to 5.
8. The lithium ion positive electrode material according to claim 7, wherein the lithium ion positive electrode material is prepared by a method comprising: and mixing and stirring the composite conductive agent, the positive active material and the adhesive according to the proportion to obtain slurry which is the lithium ion positive material.
9. The lithium ion positive electrode material according to claim 8, wherein the positive electrode active material is LiNi1-x- yCoxMnyO2Wherein 0 is<x≤0.34，0<y is less than or equal to 0.34, and the composite conductive agent accounts for 8-10% of the total mass of the lithium ion anode material.
10. A lithium ion battery comprising the lithium ion positive electrode material according to claim 7.
CN202010219218.1A 2020-03-25 2020-03-25 Composite conductive agent, lithium ion positive electrode material prepared from composite conductive agent and lithium ion battery Pending CN111525133A (en)

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Application publication date: 20200811