CN107749477A - A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries - Google Patents

A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries Download PDF

Info

Publication number
CN107749477A
CN107749477A CN201610911329.2A CN201610911329A CN107749477A CN 107749477 A CN107749477 A CN 107749477A CN 201610911329 A CN201610911329 A CN 201610911329A CN 107749477 A CN107749477 A CN 107749477A
Authority
CN
China
Prior art keywords
negative
parts
nickel cobalt
cobalt manganese
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201610911329.2A
Other languages
Chinese (zh)
Inventor
杜小红
李凡群
苏文俊
赵星星
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanxiang Group Corp
Wanxiang A123 Systems Asia Co Ltd
Original Assignee
Wanxiang Group Corp
Wanxiang A123 Systems Asia Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanxiang Group Corp, Wanxiang A123 Systems Asia Co Ltd filed Critical Wanxiang Group Corp
Priority to CN201610911329.2A priority Critical patent/CN107749477A/en
Publication of CN107749477A publication Critical patent/CN107749477A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 present invention relates to field of lithium ion battery, discloses a kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries, including positive pole and negative pole；Positive electrode includes 93 95 parts of nickel cobalt manganese NCM ternary materials, 3.5 4.5 parts of positive conductive agent, 23 parts of positive electrode binder, 15 25 parts of lytic agent；Negative material includes：94 96 parts of negative pole granular materials, 0.9 1.2 parts of cathode conductive agent, 2 2.4 parts of thickener, 2 2.4 parts of negative electrode binder；Negative pole granular materials has core shell structure, and nuclear material is Delanium, and shell material is unformed charcoal.Positive electrode of the present invention is worked good with negative material；And negative material particle is small, adhesive force and uniformity of the negative material on copper foil are good, and contact internal resistance is low.Make in after lithium ion battery, not only reduce the internal resistance of cell, and the cryogenic property, high-temperature behavior and cycle performance of battery can also be improved.

Description

A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries.
Background technology
With energy environment protection realize gradual reinforcement, in recent years new-energy automobile obtained significant progress.Wherein, it is electronic Automobile is one of Main way.And in the electrokinetic cell of electric automobile, lithium ion battery occupies very important status.
In lithium-ion-power cell, LiMn2O4 is one of selection of positive active material.
Chinese invention patent such as Application No. CN201310726770.X discloses a kind of lithium ion battery with long high temperature Circulate the preparation method of nickle cobalt lithium manganate NCM523 ternary materials.The change of long high temperature circulation nickle cobalt lithium manganate NCM523 ternary materials Formula is Li1+xNi0.5Co0.2Mn0.3AlxO2, wherein x=0.02~0.1.This method in material sintering process by aluminium salt or its Oxide adds, and is sintered again after being well mixed using dry method batch mixing, nickle cobalt lithium manganate is improved by Al ion dopings NCM523 high-temperature behavior, solve thing problems, such as that nickle cobalt lithium manganate high temperature cyclic performance, high-temperature storage performance are poor.This Invention is adulterated using dry mixed, the nickel-cobalt lithium manganate cathode material specific capacity of preparation is big, good cycle, stay in grade, into This is low, preparation technology is simple,.Pollute small, do not produce waste water, it is easy to accomplish industrialization.
But the nickel cobalt manganese NCM ternary materials lithium-ion-power cell of prior art there is also it is certain the defects of, for example, Negative material generally elects graphite as, and the cooperation of nickel cobalt manganese NCM ternary materials positive electrode and negative material is not ideal enough；In addition bear Pole material granule is big, negative material adhesive force and the uniformity on copper foil are poor the problem of, and then can cause the internal resistance of cell compared with Height, cryogenic property, high temperature discharge performance, the problem of cycle performance is poor.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries. The present invention selects nickel cobalt manganese NCM ternary materials as positive active material, from special hud typed carbon material as negative pole material Material, positive electrode are worked good with negative material；And negative material particle is small, adhesive force and uniformity of the negative material on copper foil Good, contact internal resistance is low.Make be in lithium ion battery after, not only reduce the internal resistance of cell, and can also improve battery cryogenic property, High-temperature behavior and cycle performance.
The present invention concrete technical scheme be：A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries, including positive pole and Negative pole, the positive pole include plus plate current-collecting body and positive electrode, and the negative pole includes negative current collector and negative material.By weight Part meter, the positive electrode include nickel cobalt manganese NCM ternary material 93-95 parts, positive conductive agent 3.5-4.5 parts, positive electrode binder 2-3 parts, lytic agent 15-25 parts.
The negative material includes：Negative pole granular materials 94-96 parts, cathode conductive agent 0.9-1.2 parts, thickener 2-2.4 Part, negative electrode binder 2-2.4 parts；The negative pole granular materials has a nucleocapsid structure, and wherein nuclear material is Delanium, shell material Expect for unformed charcoal.
The present invention, as positive active material, is made from nickel cobalt manganese NCM ternary materials from special hud typed carbon material For negative material, positive electrode is worked good with negative material；And negative material particle is small, adhesive force of the negative material on copper foil Good with uniformity, contact internal resistance is low.Make in after lithium ion battery, not only reduce the internal resistance of cell, and battery can also be improved Cryogenic property, high-temperature behavior and cycle performance.
Preferably, the particle diameter of the negative pole granular materials is d50≤6μm。
Preferably, the negative electrode binder is 1 by mass ratio:1-2 carboxymethyl cellulose and butadiene-styrene rubber composition, its Described in butadiene-styrene rubber be that particle diameter is less than 0.2 μm of styrol copolymer, the pH values of butadiene-styrene rubber are 6.5-7.5.
It is good with the bonding effect of collector after above-mentioned negative electrode binder and other specific components in the present invention are compound, no It is easy to fall off.
Preferably, the preparation method of the negative pole granular materials comprises the following steps：
1）By coal tar and pitch 5-50 in mass ratio:1 mixes at 75-85 DEG C, and being heated to 400-430 DEG C after well mixed enters Row heat polymerization 2-4h；
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 350-420 DEG C, vacuum for- 0.10 to -0.08MPa, time 0.5-1.5h；
3）By step 2）Product at 2800-3000 DEG C graphitization processing 4-8h, obtain Delanium；
4）Soft carbon or hard carbon are added into the Delanium, is added under atmosphere of inert gases in polybenzazole precursor liquid solution Organic liquid phase cladding processing is carried out, obtains carbon polymer cladding organic double compound, high temperature is then carried out at 600-1700 DEG C forges Burning processing, constant temperature keep 0.5-48h, obtain charcoal bag and cover negative material；
5）Negative material being covered to the charcoal bag charing process is carried out under atmosphere of inert gases, carbonization temperature is 800-1200 DEG C, Carbonization time is 4-6h；Then carbonizing production is crushed, be classified after crushing by particle diameter, obtain negative pole granular materials.
The present invention from selection with good rate capability and the excellent raw material of cycle performance, after carrying out thermal polymerization, then low temperature Modification, the individual particle structural artificial's graphite for the specified particle diameter that then high-temperature heat treatment obtains, its high rate during charging-discharging It is good, the small particle Delanium base material of densification is prepared into, there is good high rate during charging-discharging and cycle life.
Negative pole granular materials is act as：
1st, short grained negative pole granular materials can shorten lithium ion diffusion length, increase electrolyte wetted area, reduce pole piece OI values, so as to effectively lift the multiplying power and power-performance of material.
2nd, there is coarse surface with pure Delanium, electrochemical reaction activity is higher, increases the consumption of electrolyte, and After unformed charcoal bag covers Delanium, surface is relatively smooth after cladding, and surface forms amorphous carbon coating, reduces active site；Simultaneously The electrode reaction resistance of material can be greatly lowered, the power and cryogenic property for making material get a promotion.
3rd, after cycling, internal structure can become loose not fine and close to pure Delanium, and can avoid this feelings after coating Condition, fine and close internal structure and smooth surface texture can effectively extend the cycle life of lithium battery.
Carried out on the basis of individual particle Delanium it is granule modified, it is unformed by liquid phase coating on Delanium surface Charcoal, make it have nucleocapsid structure, it is therefore an objective to further improve interface resistance, lift cryogenic property and power characteristic.Using liquid phase Cladding, is evenly coated, carbon residue is low.
Preferably, step 3）In, the graphitization processing time is 5h.
Preferably, step 4）In, Delanium is 1 with the mass ratio of soft carbon or hard carbon:0.01-15, the high temperature are forged The temperature for burning processing is 1200 DEG C, thermostatic hold-time 24h.
Preferably, step 4）In, the polybenzazole precursor liquid solution is Water-soluble phenolic resin solution.
Preferably, the negative material also includes carbon/silicon composite sol 3-5 parts.
Carbon/silicon composite sol can form solid skeletal in solidification, and the skeleton has loose pore passage structure, the pore passage structure The infiltration of electrolyte is not only contributed to, strengthens electric conductivity, reduces internal resistance, and the firm work of auxiliary can be played to active material With negative material after solidification is not easy to crack, comes off, high with the adhesive fastness of collector.
Preferably, the preparation method of the carbon/Ludox is as follows：
a）By tetraethyl orthosilicate, absolute ethyl alcohol, toluene 8-10 in mass ratio:100:0.1-0.2 is mixed, obtained solution A；By 0.5- 1.5mol/L glacial acetic acid, absolute ethyl alcohol and water 20-30 in mass ratio:100:6-8 is mixed, obtained solution B；To solution A Supersonic oscillations processing is carried out at 50-60 DEG C, solution B is added drop-wise to its 3-4 times of quality with 0.5-1.0 mL/s speed In solution A；0.01-0.03 times of the sodium acid carbonate that quality is solution A is added while solution B is added dropwise into solution A, is dripped 2-4h is stirred after finishing, Ludox is made；
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 1-3:1 carbon/silicon is compound Colloidal sol.
Ludox prepared by the above method is mixed in specific proportions with nano carbon sol, converged in Ludox preparation process Always, pore-foaming agent is added, more pore passage structures can be formed after colloidal sol solidification, be further advantageous to the infiltration of electrolyte, increase Strong electric conductivity, reduce internal resistance.
Preferably, the preparation method of the negative material comprises the following steps：
A）Negative pole granular materials, cathode conductive agent, negative electrode binder, carbon/silicon composite sol are uniformly mixed according to a ratio, addition is molten 2-4 times of dilution agent, obtains cathode size；
B）By the cathode size coated on negative current collector, roll-in is then carried out, then the aging 4-8h at 40-50 DEG C；
C）Negative current collector is warming up into 80-120 DEG C under vacuum after aging to be dried, after cathode size curing molding Negative material is made.
It is coated after cathode size is made, cathode size is carried out aging after roll-in, the purpose of aging is to make negative pole The loose pore passage structure under its collosol state can be kept after slurry curing as far as possible, heating drying is carried out again after aging shaping, it is molten Agent moment is volatilized, and shaping structures, loose pore passage structure is retained.
It is compared with the prior art, the beneficial effects of the invention are as follows：The present invention is from nickel cobalt manganese NCM ternary materials as positive pole Active material, worked good from special hud typed carbon material as negative material, positive electrode with negative material；And negative pole material Expect that particle is small, adhesive force and uniformity of the negative material on copper foil are good, and contact internal resistance is low.Make be in lithium ion battery after, no But the internal resistance of cell is reduced, and the cryogenic property, high-temperature behavior and cycle performance of battery can also be improved.
Brief description of the drawings
Fig. 1 is the cryogenic property data comparison figure of battery made from negative material of the present invention and prior art battery；
Fig. 2 is the high-temperature behavior data comparison figure of battery made from negative material of the present invention and prior art battery.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries, including positive pole and negative pole.
The positive pole includes plus plate current-collecting body and positive electrode, and the negative pole includes negative current collector and negative material；Press Parts by weight meter, the positive electrode include 94 parts of nickel cobalt manganese NCM ternary materials, 4 parts of positive conductive agent, 2.5 parts of positive electrode binder, 20 parts of lytic agent.
The negative material includes：95 parts of negative pole granular materials, 2 parts of cathode conductive agent, 2.2 parts of thickener, negative pole bonding 3 parts of agent；The negative pole granular materials has nucleocapsid structure, and wherein nuclear material is Delanium, and shell material is unformed charcoal.
Wherein, the negative electrode binder is 1 by mass ratio:1.5 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein institute The styrol copolymer that butadiene-styrene rubber is less than 0.2 μm for particle diameter is stated, the pH values of butadiene-styrene rubber are 6.5-7.5.
The negative pole granular materials has nucleocapsid structure, and wherein nuclear material is Delanium, and shell material is unformed charcoal, The particle diameter of negative pole granular materials is d50≤6μm。
The preparation method of the negative pole granular materials comprises the following steps：
1）By coal tar and pitch in mass ratio 28:1 is mixed at 80 DEG C, and 415 DEG C of progress thermal polymerizations are heated to after well mixed React 3h.
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 385 DEG C, vacuum for- 0.10 to -0.08MPa, time 1h.
3）By step 2）Product at 2900 DEG C graphitization processing 5h, obtain Delanium
4）Add soft carbon into the Delanium, the mass ratio of Delanium and soft carbon is 1:7.5, under atmosphere of inert gases Progress organic liquid phase cladding processing in Water-soluble phenolic resin solution is added to, obtains carbon polymer cladding organic double compound, so High-temperature calcination processing is carried out at 1200 DEG C afterwards, constant temperature keeps 24h, obtains charcoal bag and cover negative material.
5）Negative material being covered to the charcoal bag charing process is carried out under atmosphere of inert gases, carbonization temperature is 1000 DEG C, Carbonization time is 5h；Then carbonizing production is crushed, be classified after crushing by particle diameter, obtain negative pole granular materials.
Embodiment 2
A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries, including positive pole and negative pole.
The positive pole includes plus plate current-collecting body and positive electrode, and the negative pole includes negative current collector and negative material；Press Parts by weight meter, the positive electrode include 94 parts of nickel cobalt manganese NCM ternary materials, 4 parts of positive conductive agent, 2.5 parts of positive electrode binder, 20 parts of lytic agent.
The negative material includes：95 parts of negative pole granular materials, 1.1 parts of cathode conductive agent, 2.2 parts of thickener, negative pole glues 2.2 parts of mixture, 4 parts of carbon/silicon composite sol；The negative pole granular materials has nucleocapsid structure, and wherein nuclear material is artificial stone Ink, shell material are unformed charcoal.
Wherein, the negative electrode binder is 1 by mass ratio:1.5 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein institute The styrol copolymer that butadiene-styrene rubber is less than 0.2 μm for particle diameter is stated, the pH values of butadiene-styrene rubber are 6.5-7.5.
The negative pole granular materials has nucleocapsid structure, and wherein nuclear material is Delanium, and shell material is unformed charcoal, The particle diameter of negative pole granular materials is d50≤6μm。
The preparation method of the negative pole granular materials comprises the following steps：
1）By coal tar and pitch in mass ratio 25:1 is mixed at 80 DEG C, and 410 DEG C of progress thermal polymerizations are heated to after well mixed React 3h.
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 380 DEG C, vacuum for- 0.10 to -0.08MPa, time 1h.
3）By step 2）Product at 2900 DEG C graphitization processing 6h, obtain Delanium；
4）Add hard carbon into the Delanium, the mass ratio of Delanium and hard carbon is 1:6, add under atmosphere of inert gases Enter into Water-soluble phenolic resin solution and carry out organic liquid phase cladding processing, obtain carbon polymer cladding organic double compound, then High-temperature calcination processing is carried out at 1300 DEG C, constant temperature keeps 20h, obtains charcoal bag and cover negative material.
5）Negative material being covered to the charcoal bag charing process is carried out under atmosphere of inert gases, carbonization temperature is 1000 DEG C, Carbonization time is 5h；Then carbonizing production is crushed, be classified after crushing by particle diameter, obtain negative pole granular materials.
The preparation method of the carbon/Ludox is as follows：
a）By tetraethyl orthosilicate, absolute ethyl alcohol, toluene in mass ratio 9:100:0.15 mixing, obtained solution A；By 1mol/L ice Acetic acid, absolute ethyl alcohol and water in mass ratio 25:100:7 are mixed, obtained solution B；Ultrasonic wave is carried out at 55 DEG C to solution A Oscillation treatment, solution B is added drop-wise in the solution A of its 3.5 times of quality with 0.75mL/s speed；Be added dropwise solution B while to 0.02 times of the sodium acid carbonate that quality is solution A is added in solution A, 3h is stirred after being added dropwise, Ludox is made.
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 2:1 carbon/silicon is multiple Close colloidal sol.
The preparation method of above-mentioned negative material, comprises the following steps：
A）Negative pole granular materials, cathode conductive agent, negative electrode binder, carbon/silicon composite sol are uniformly mixed according to a ratio, addition is molten 3 times of dilution agent, obtains cathode size
B）By the cathode size coated on negative current collector, roll-in is then carried out, then the aging 6h at 45 DEG C.
C）Negative current collector is warming up into 100 DEG C under vacuum after aging to be dried, cathode size curing molding Negative material is made afterwards.
Embodiment 3
A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries, including positive pole and negative pole.
The positive pole includes plus plate current-collecting body and positive electrode, and the negative pole includes negative current collector and negative material；Press Parts by weight meter, the positive electrode include 93 parts of nickel cobalt manganese NCM ternary materials, 3.5 parts of positive conductive agent, 2 parts of positive electrode binder, 15 parts of lytic agent.
The negative material includes：94 parts of negative pole granular materials, 0.9 part of cathode conductive agent, 2 parts of thickener, negative pole bonding 2 parts of agent, 3 parts of carbon/silicon composite sol；The negative pole granular materials has a nucleocapsid structure, and wherein nuclear material is Delanium, shell Material is unformed charcoal.
Wherein, the negative electrode binder is 1 by mass ratio:2 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein described Butadiene-styrene rubber is the styrol copolymer that particle diameter is less than 0.2 μm, and the pH values of butadiene-styrene rubber are 6.5-7.5.
The negative pole granular materials has nucleocapsid structure, and wherein nuclear material is Delanium, and shell material is unformed charcoal, The particle diameter of negative pole granular materials is d50≤6μm。
The preparation method of the negative pole granular materials comprises the following steps：
1）By coal tar and pitch in mass ratio 50:1 is mixed at 85 DEG C, and 430 DEG C of progress thermal polymerizations are heated to after well mixed React 2h.
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 420 DEG C, vacuum for- 0.10 to -0.08MPa, time 0.5h.
3）By step 2）Product at 3000 DEG C graphitization processing 4h, obtain Delanium.
4）Add soft carbon into the Delanium, the mass ratio of Delanium and soft carbon is 1:0.01, in inert gas Progress organic liquid phase cladding processing in Water-soluble phenolic resin solution is added under atmosphere, obtains carbon polymer cladding organic composite Thing, then carries out high-temperature calcination processing at 1700 DEG C, and constant temperature keeps 0.5h, obtains charcoal bag and cover negative material.
5）Negative material being covered to the charcoal bag charing process is carried out under atmosphere of inert gases, carbonization temperature is 1200 DEG C, Carbonization time is 4h；Then carbonizing production is crushed, be classified after crushing by particle diameter, obtain negative pole granular materials.
The preparation method of the carbon/Ludox is as follows：
a）By tetraethyl orthosilicate, absolute ethyl alcohol, toluene in mass ratio 10:100:0.2 mixing, obtained solution A；By 1.5mol/L's Glacial acetic acid, absolute ethyl alcohol and water in mass ratio 30:100:8 are mixed, obtained solution B；Ultrasound is carried out at 60 DEG C to solution A Ripple oscillation treatment, solution B is added drop-wise in the solution A of its 4 times of quality with 1.0 mL/s speed；Be added dropwise solution B while to 0.03 times of the sodium acid carbonate that quality is solution A is added in solution A, 4h is stirred after being added dropwise, Ludox is made.
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 3:1 carbon/silicon is multiple Close colloidal sol.
The preparation method of above-mentioned negative material, comprises the following steps：
A）Negative pole granular materials, cathode conductive agent, negative electrode binder, carbon/silicon composite sol are uniformly mixed according to a ratio, addition is molten 4 times of dilution agent, obtains cathode size；
B）By the cathode size coated on negative current collector, roll-in is then carried out, then the aging 4h at 50 DEG C；
C）Negative current collector is warming up into 120 DEG C under vacuum after aging to be dried, made after cathode size curing molding Obtain negative material.
Embodiment 4
A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries, including positive pole and negative pole.
The positive pole includes plus plate current-collecting body and positive electrode, and the negative pole includes negative current collector and negative material；Press Parts by weight meter, the positive electrode include 95 parts of nickel cobalt manganese NCM ternary materials, 4.5 parts of positive conductive agent, 3 parts of positive electrode binder, 25 parts of lytic agent.
The negative material includes：96 parts of negative pole granular materials, 1.2 parts of cathode conductive agent, 2.4 parts of thickener, negative pole glues 2.4 parts of mixture, 5 parts of carbon/silicon composite sol；The negative pole granular materials has nucleocapsid structure, and wherein nuclear material is artificial stone Ink, shell material are unformed charcoal.
Wherein, the negative electrode binder is 1 by mass ratio:1 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein described Butadiene-styrene rubber is the styrol copolymer that particle diameter is less than 0.2 μm, and the pH values of butadiene-styrene rubber are 6.5-7.5.
The negative pole granular materials has nucleocapsid structure, and wherein nuclear material is Delanium, and shell material is unformed charcoal, The particle diameter of negative pole granular materials is d50≤6μm。
The preparation method of the negative pole granular materials comprises the following steps：
1）By coal tar and pitch in mass ratio 5:1 is mixed at 75 DEG C, and it is anti-that 400 DEG C of progress thermal polymerizations are heated to after well mixed Answer 4h.
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 350 DEG C, vacuum for- 0.10 to -0.08MPa, time 1.5h.
3）By step 2）Product at 2800 DEG C graphitization processing 8h, obtain Delanium.
4）Add hard carbon into the Delanium, the mass ratio of Delanium and hard carbon is 1:15, in inert gas atmosphere Progress organic liquid phase cladding processing in Water-soluble phenolic resin solution is added under enclosing, obtains carbon polymer cladding organic composite Thing, then carries out high-temperature calcination processing at 600 DEG C, and constant temperature keeps 48h, obtains charcoal bag and cover negative material.
5）Negative material being covered to the charcoal bag charing process is carried out under atmosphere of inert gases, carbonization temperature is 800- DEG C, Carbonization time is 6h；Then carbonizing production is crushed, be classified after crushing by particle diameter, obtain negative pole granular materials.
The preparation method of the carbon/Ludox is as follows：
a）By tetraethyl orthosilicate, absolute ethyl alcohol, toluene in mass ratio 8:100:0.1 mixing, obtained solution A；By 0.5mol/L's Glacial acetic acid, absolute ethyl alcohol and water in mass ratio 20:100:6 are mixed, obtained solution B；Ultrasound is carried out at 50 DEG C to solution A Ripple oscillation treatment, solution B is added drop-wise in the solution A of its 3 times of quality with 0.5 mL/s speed；Be added dropwise solution B while to 0.01 times of the sodium acid carbonate that quality is solution A is added in solution A, 2h is stirred after being added dropwise, Ludox is made.
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 1:1 carbon/silicon is multiple Close colloidal sol.
The preparation method of above-mentioned negative material, comprises the following steps：
A）Negative pole granular materials, cathode conductive agent, negative electrode binder, carbon/silicon composite sol are uniformly mixed according to a ratio, addition is molten 2 times of dilution agent, obtains cathode size.
B）By the cathode size coated on negative current collector, roll-in is then carried out, then the aging 8h at 40 DEG C；
C）Negative current collector is warming up into 120 DEG C under vacuum after aging to be dried, made after cathode size curing molding Obtain negative material.
Performance test
Performance test is carried out to the lithium-ion-power cell of embodiment 1, is by conventional artificial's graphite, positive electrode of negative material Two kinds of lithium-ion-power cells of nickel cobalt manganese NCM ternary materials are comparative example 1, comparative example 2, carry out performance test.
1st, cryogenic property compares：Cryogenic property test, test result are carried out to embodiment 1, comparative example 1-2 at -25 DEG C As shown in Figure 1, it is seen that 1 cryogenic property of embodiment is preferable.
2nd, high-temperature behavior compares：High-temperature behavior test is carried out to embodiment 1, comparative example 1-2 at 55 DEG C, test result is such as Shown in Fig. 2, it is seen that the capability retention at high temperature of the 1 of embodiment and capacity response rate are higher, respectively reach 95.05% With 96.12%.
Raw materials used in the present invention, equipment, it is the conventional raw material, equipment of this area unless otherwise noted；In the present invention Method therefor, it is the conventional method of this area unless otherwise noted.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention Any simple modification, change and the equivalent transformation that technical spirit is made to above example, still fall within the technology of the present invention side The protection domain of case.

Claims (10)

1. a kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries, including positive pole and negative pole, the positive pole include anode collection Body and positive electrode, the negative pole include negative current collector and negative material；It is characterized in that：By weight, the positive pole Material includes nickel cobalt manganese NCM ternary material 93-95 parts, positive conductive agent 3.5-4.5 parts, positive electrode binder 2-3 parts, lytic agent 15-25 parts；
The negative material includes：Negative pole granular materials 94-96 parts, cathode conductive agent 0.9-1.2 parts, thickener 2-2.4 parts, bear Very viscous mixture 2-2.4 parts；The negative pole granular materials has nucleocapsid structure, and wherein nuclear material is Delanium, and shell material is nothing Sizing charcoal.
2. a kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that described negative The particle diameter of pole granular materials is d50≤6μm。
3. a kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that described negative Very viscous mixture is 1 by mass ratio:1-2 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein the butadiene-styrene rubber is that particle diameter is small In 0.2 μm of styrol copolymer, the pH values of butadiene-styrene rubber are 6.5-7.5.
4. a kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that described negative The preparation method of pole granular materials comprises the following steps：
1）By coal tar and pitch 5-50 in mass ratio:1 mixes at 75-85 DEG C, and being heated to 400-430 DEG C after well mixed enters Row heat polymerization 2-4h；
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 350-420 DEG C, vacuum for- 0.10 to -0.08MPa, time 0.5-1.5h；
3）By step 2）Product at 2800-3000 DEG C graphitization processing 4-8h, obtain Delanium；
4）Soft carbon or hard carbon are added into the Delanium, is added under atmosphere of inert gases in polybenzazole precursor liquid solution Organic liquid phase cladding processing is carried out, obtains carbon polymer cladding organic double compound, high temperature is then carried out at 600-1700 DEG C forges Burning processing, constant temperature keep 0.5-48h, obtain charcoal bag and cover negative material；
5）Negative material being covered to the charcoal bag charing process is carried out under atmosphere of inert gases, carbonization temperature is 800-1200 DEG C, Carbonization time is 4-6h；Then carbonizing production is crushed, be classified after crushing by particle diameter, obtain negative pole granular materials.
A kind of 5. nickel cobalt manganese NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that step 3） In, the graphitization processing time is 5h.
A kind of 6. nickel cobalt manganese NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that step 4） In, Delanium is 1 with the mass ratio of soft carbon or hard carbon:0.01-15, the temperature of the high-temperature calcination processing is 1200 DEG C, permanent The warm retention time is 24h.
A kind of 7. nickel cobalt manganese NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that step 4） In, the polybenzazole precursor liquid solution is Water-soluble phenolic resin solution.
A kind of 8. nickel cobalt manganese NCM ternary material power lithium-ion batteries as described in claim 1-7 is any, it is characterised in that The negative material also includes carbon/silicon composite sol 3-5 parts.
A kind of 9. nickel cobalt manganese NCM ternary material power lithium-ion batteries as claimed in claim 8, it is characterised in that the carbon/ The preparation method of Ludox is as follows：
a）By tetraethyl orthosilicate, absolute ethyl alcohol, toluene 8-10 in mass ratio:100:0.1-0.2 is mixed, obtained solution A；By 0.5- 1.5mol/L glacial acetic acid, absolute ethyl alcohol and water 20-30 in mass ratio:100:6-8 is mixed, obtained solution B；To solution A Supersonic oscillations processing is carried out at 50-60 DEG C, solution B is added drop-wise to its 3-4 times of quality with 0.5-1.0 mL/s speed In solution A；0.01-0.03 times of the sodium acid carbonate that quality is solution A is added while solution B is added dropwise into solution A, is dripped 2-4h is stirred after finishing, Ludox is made；
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 1-3:1 carbon/silicon is compound Colloidal sol.
10. a kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries as claimed in claim 8, it is characterised in that described negative The preparation method of pole material comprises the following steps：
A）Negative pole granular materials, cathode conductive agent, negative electrode binder, carbon/silicon composite sol are uniformly mixed according to a ratio, addition is molten 2-4 times of dilution agent, obtains cathode size；
B）By the cathode size coated on negative current collector, roll-in is then carried out, then the aging 4-8h at 40-50 DEG C；
C）Negative current collector is warming up into 80-120 DEG C under vacuum after aging to be dried, after cathode size curing molding Negative material is made.
CN201610911329.2A 2016-10-19 2016-10-19 A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries Withdrawn CN107749477A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610911329.2A CN107749477A (en) 2016-10-19 2016-10-19 A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610911329.2A CN107749477A (en) 2016-10-19 2016-10-19 A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries

Publications (1)

Publication Number Publication Date
CN107749477A true CN107749477A (en) 2018-03-02

Family

ID=61255368

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610911329.2A Withdrawn CN107749477A (en) 2016-10-19 2016-10-19 A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries

Country Status (1)

Country Link
CN (1) CN107749477A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111048749A (en) * 2019-10-30 2020-04-21 深圳市卓能新能源股份有限公司 Negative pole piece, lithium ion battery and manufacturing method thereof
CN114188517A (en) * 2021-11-29 2022-03-15 万华化学(四川)有限公司 Preparation method of novel ternary cathode material, lithium battery prepared from cathode material and application of cathode material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1339838A (en) * 2000-08-22 2002-03-13 中国科学院化学研究所 Carbon negative electrode material of lithium ion cell and its preparing method and use
CN103887473A (en) * 2014-04-20 2014-06-25 天津市捷威动力工业有限公司 Negative electrode with surface coated with lithiated zeolite and lithium ion battery using negative electrode
CN103887502A (en) * 2012-12-21 2014-06-25 上海杉杉科技有限公司 Artificial graphite lithium ion battery anode material and preparation method thereof
CN104659366A (en) * 2014-12-30 2015-05-27 东莞市凯金新能源科技有限公司 Preparation method of anode material for power lithium ion battery
CN104766962A (en) * 2015-04-17 2015-07-08 辽宁工程技术大学 Preparation method of carbon-cladding graphite oxide/Sn composite cathode material of lithium ion battery
CN105854818A (en) * 2016-03-24 2016-08-17 浙江海洋学院 Aerogel-based oil eliminating agent and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1339838A (en) * 2000-08-22 2002-03-13 中国科学院化学研究所 Carbon negative electrode material of lithium ion cell and its preparing method and use
CN103887502A (en) * 2012-12-21 2014-06-25 上海杉杉科技有限公司 Artificial graphite lithium ion battery anode material and preparation method thereof
CN103887473A (en) * 2014-04-20 2014-06-25 天津市捷威动力工业有限公司 Negative electrode with surface coated with lithiated zeolite and lithium ion battery using negative electrode
CN104659366A (en) * 2014-12-30 2015-05-27 东莞市凯金新能源科技有限公司 Preparation method of anode material for power lithium ion battery
CN104766962A (en) * 2015-04-17 2015-07-08 辽宁工程技术大学 Preparation method of carbon-cladding graphite oxide/Sn composite cathode material of lithium ion battery
CN105854818A (en) * 2016-03-24 2016-08-17 浙江海洋学院 Aerogel-based oil eliminating agent and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111048749A (en) * 2019-10-30 2020-04-21 深圳市卓能新能源股份有限公司 Negative pole piece, lithium ion battery and manufacturing method thereof
CN111048749B (en) * 2019-10-30 2022-01-14 深圳市卓能新能源股份有限公司 Negative pole piece, lithium ion battery and manufacturing method thereof
CN114188517A (en) * 2021-11-29 2022-03-15 万华化学(四川)有限公司 Preparation method of novel ternary cathode material, lithium battery prepared from cathode material and application of cathode material
CN114188517B (en) * 2021-11-29 2023-12-29 万华化学(四川)有限公司 Preparation method of ternary positive electrode material, lithium battery prepared from positive electrode material and application of lithium battery

Similar Documents

Publication Publication Date Title
CN104638240B (en) Method for preparing lithium ion battery silicon carbon composite anode material and product prepared by method
CN106848264A (en) A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof
CN108511685A (en) A kind of anode plate for lithium ionic cell and preparation method thereof containing conductive coating
CN109449385B (en) Carbon-coated amorphous silicon/graphene composite negative electrode material, preparation method thereof and lithium ion battery
CN108511689A (en) A kind of based lithium-ion battery positive plate and preparation method thereof containing conductive coating
CN110504430A (en) A kind of lithium ion battery silicon-carbon cathode material and preparation method thereof
CN110752356B (en) Preparation method of sodium ion battery anode material of double-metal selenide
CN106558729B (en) A kind of lithium ion battery of graphene as anode sizing agent conductive agent
CN112670461B (en) Natural graphite carbon coated negative electrode material, preparation method thereof and lithium ion battery
CN109626352A (en) A kind of high multiplying power lithium ion battery class hard carbon graphite cathode material and preparation method thereof
CN107464938B (en) Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery
CN113745465B (en) Preparation method of silicon-carbon composite material
CN112490403B (en) Pole piece with uniform thickness of lug ceramic coating and preparation method thereof
CN106299344B (en) A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof
CN101355150B (en) Method for preparing graphitic carbon nanometer tube combination electrode material for lithium ion battery
CN107749465A (en) A kind of LiFePO4 NCM ternary material power lithium-ion batteries
CN107749478A (en) A kind of LiMn2O4 ternary power lithium ion battery
CN111653734A (en) Ferrosilicon/carbon composite lithium ion battery cathode material and preparation method and application thereof
CN107749462A (en) A kind of high-performance lithium ion power battery cathode material
CN113998700A (en) Method for preparing Si/SiC @ C anode material by using micro silicon powder as raw material
CN113644243A (en) Nitrogen-doped hollow-structure graphite microsphere, composite negative electrode material and preparation method of composite negative electrode material
CN109494345A (en) A kind of battery preparation method and battery promoting lithium ion battery safety performance
CN109686941A (en) A method of preparing lithium-ion-power cell silicon-carbon cathode material
CN103395846A (en) Preparation method and application of octahedron-shaped cobaltosic oxide anode material for lithium ion battery
CN107749477A (en) A kind of nickel cobalt manganese NCM ternary material power lithium-ion batteries

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20180302