CN107749465A - A kind of LiFePO4 NCM ternary material power lithium-ion batteries - Google Patents
A kind of LiFePO4 NCM ternary material power lithium-ion batteries Download PDFInfo
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- CN107749465A CN107749465A CN201610947009.2A CN201610947009A CN107749465A CN 107749465 A CN107749465 A CN 107749465A CN 201610947009 A CN201610947009 A CN 201610947009A CN 107749465 A CN107749465 A CN 107749465A
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- 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
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- H—ELECTRICITY
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- 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
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- 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
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- 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
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- 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
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 LiFePO4 NCM ternary material power lithium-ion batteries, and positive electrode includes 91 93 parts of positive active material, 46 parts of positive conductive agent, 24 parts of positive electrode binder, 15 25 parts of lytic agent；Positive active material is the composite of LiFePO4 and nickel cobalt manganese NCM ternary materials；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 wherein 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.After being fabricated to lithium ion battery, the internal resistance of cell is not only reduced, and the cryogenic property, high-temperature behavior and cycle performance of battery can also be improved.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of LiFePO4-NCM ternary materials lithium ion power electricity
Pond.
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, LiFePO4 and NCM ternary materials are one of selections of positive active material.
Chinese invention patent such as Application No. CN201410654321.3 discloses a kind of LiFePO4 and nickel cobalt phosphoric acid
The preparation method of iron lithium composite positive pole, positive active material includes LiFePO4 and nickel cobalt LiFePO4, by both
Mixing and ball milling is carried out with conductive agent respectively, pre-coated is carried out, both is mixed after pre-coated, then uses dry method again（It is or wet
Method）Ball milling, it is dried, crushes, is classified, the rear anode composite material for obtaining Surface coating LiFePO4 and nickel cobalt LiFePO4
Material.The present invention improves the problem of cycle performance of nickel cobalt ferric phosphate lithium ion battery is with super-charge super-discharge electricity, extends battery
Service life.The positive electrode is that LiFePO4 mixes with nickel cobalt LiFePO4, without preparing new material, as long as by both
Positive electrode be well mixed, therefore will not substantially increase cost.
But the LiFePO4 of prior art-ternary lithium-ion-power cell there is also it is certain the defects of, for example, negative pole
Material generally elects graphite as, and the cooperation of LiFePO4-tertiary cathode material and negative material is not ideal enough；In addition negative material
Grain is big, negative material can cause the internal resistance of cell higher adhesive force and the uniformity on copper foil are poor the problem of, low temperature properties
Energy, 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 LiFePO4-NCM ternary materials lithium ion power electricity
Pond.The present invention selects LiFePO4-NCM ternary materials as positive active material, from special hud typed carbon material conduct
Negative material, positive electrode are worked good with negative material；And negative material particle is small, adhesive force of the negative material on copper foil and
Uniformity is good, and contact internal resistance is low.After being fabricated to lithium ion battery, the internal resistance of cell is not only reduced, and the low of battery can also be improved
Warm nature energy, high-temperature behavior and cycle performance.
The present invention concrete technical scheme be：A kind of LiFePO4-NCM ternary material power lithium-ion batteries, including just
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；Press
Parts by weight meter, the positive electrode include positive active material 91-93 parts, positive conductive agent 4-6 parts, positive electrode binder 2-4 parts,
Lytic agent 15-25 parts；The positive active material is the composite of LiFePO4 and nickel cobalt manganese NCM ternary materials.
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 selects LiFePO4 with nickel cobalt manganese NCM ternary materials as positive active material, from special nucleocapsid
Type carbon material is worked good as negative material, positive electrode with negative material；And negative material particle is small, negative material is in copper foil
On adhesive force and uniformity it is good, contact internal resistance it is low.After being fabricated to lithium ion battery, the internal resistance of cell is not only reduced, and can also
Improve cryogenic property, high-temperature behavior and the cycle performance of battery.
Preferably, the mol ratio of nickel cobalt manganese is 1 in the nickel cobalt manganese NCM ternary materials:1:1.
Preferably, the mass ratio of LiFePO4 and nickel cobalt manganese NCM ternary materials is 2 in the positive active material:8 or
3:7 or 4:6.
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, Water-soluble phenolic resin solution is added under atmosphere of inert gases
Middle progress organic liquid phase cladding processing, carbon polymer cladding organic double compound is obtained, high temperature is then carried out at 600-1700 DEG C
Calcination 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 is forged
The temperature for burning processing is 1200 DEG C, thermostatic hold-time 24h.
Preferably, the negative material also includes carbon/silicon composite sol 3-5 parts；The preparation method of the carbon/Ludox
It 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.
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.
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, conductive agent, negative electrode binder, carbon/silicon composite sol are uniformly mixed according to a ratio, addition solvent is dilute
2-4 times is released, 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 selects LiFePO4-NCM ternary material conducts
Positive active material, worked good from special hud typed carbon material as negative material, positive electrode with negative material；It is and negative
Pole material granule is small, and adhesive force and uniformity of the negative material on copper foil are good, and contact internal resistance is low.It is fabricated to lithium ion battery
Afterwards, the internal resistance of cell is not only reduced, and the cryogenic property, high-temperature behavior and cycle performance of battery can also be improved.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of LiFePO4-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：92 parts of positive active material, 5 parts of positive conductive agent, 3 parts of positive electrode binder, lytic agent
20 parts.The mass ratio of LiFePO4 and nickel cobalt manganese NCM ternary materials is 2 in the positive active material:8.The nickel cobalt manganese NCM
The mol ratio of nickel cobalt manganese is 1 in ternary material:1:1.
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 LiFePO4-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：92 parts of positive active material, 5 parts of positive conductive agent, 3 parts of positive electrode binder, lytic agent
20 parts.The mass ratio of LiFePO4 and nickel cobalt manganese NCM ternary materials is 2 in the positive active material:8.The nickel cobalt manganese NCM
The mol ratio of nickel cobalt manganese is 1 in ternary material:1:1.
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 LiFePO4-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：91 parts of positive active material, 4 parts of positive conductive agent, 2 parts of positive electrode binder, lytic agent
25 parts.The mass ratio of LiFePO4 and nickel cobalt manganese NCM ternary materials is 3 in the positive active material:7.The positive pole nickel cobalt
The mol ratio of nickel cobalt manganese is 1 in manganese NCM ternary materials:1:1.
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 LiFePO4-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 positive active material, 6 parts of positive conductive agent, 4 parts of positive electrode binder, lytic agent
15 parts.The mass ratio of LiFePO4 and nickel cobalt manganese NCM ternary materials is 4 in the positive active material:6.The nickel cobalt manganese NCM
The mol ratio of nickel cobalt manganese is 1 in ternary material:1:1.
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 embodiment 1-2 lithium-ion-power cell, using negative material as conventional artificial's graphite, positive electrode
Lithium-ion-power cell for LiFePO4-NCM ternary materials is comparative example 1, carries out performance test.
1st, high-temperature behavior compares：High-temperature behavior test is carried out to embodiment 1, comparative example 1 at 55 DEG C, test result is：
On battery capacity conservation rate, the embodiment 1-2 lifting of battery capacity conservation rate relative contrast example 1 8.15% and 9.58%；
On capacity resuming rate, the lifting of capacity resuming rate relative contrast example 1 7.51% and 6.81% of embodiment 1.
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 LiFePO4-NCM ternary material power lithium-ion batteries, including positive pole and negative pole, the positive pole include positive pole
Collector and positive electrode, the negative pole include negative current collector and negative material；It is characterized in that：By weight, it is described
Positive electrode includes positive active material 91-93 parts, positive conductive agent 4-6 parts, positive electrode binder 2-4 parts, lytic agent 15-25
Part；The positive active material is the composite of LiFePO4 and nickel cobalt manganese NCM ternary materials；
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 LiFePO4-NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that described
The mol ratio of nickel cobalt manganese is 1 in nickel cobalt manganese NCM ternary materials:1:1.
3. a kind of LiFePO4-NCM ternary material power lithium-ion batteries as claimed in claim 2, it is characterised in that described
The mass ratio of LiFePO4 and nickel cobalt manganese NCM ternary materials is 2 in positive active material:8 or 3:7 or 4:6.
4. a kind of LiFePO4-NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that described
The particle diameter of negative pole granular materials is d50≤6μm。
5. a kind of LiFePO4-NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that described
Negative electrode binder is 1 by mass ratio:1-2 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein the butadiene-styrene rubber is particle diameter
Styrol copolymer less than 0.2 μm, the pH values of butadiene-styrene rubber are 6.5-7.5.
6. a kind of LiFePO4-NCM ternary material power lithium-ion batteries as claimed in claim 1, it is characterised in that described
The preparation method of 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, Water-soluble phenolic resin solution is added under atmosphere of inert gases
Middle progress organic liquid phase cladding processing, carbon polymer cladding organic double compound is obtained, high temperature is then carried out at 600-1700 DEG C
Calcination 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 7. LiFePO4-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 8. LiFePO4-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,
Thermostatic hold-time is 24h.
9. a kind of LiFePO4-NCM ternary material power lithium-ion batteries as described in claim 1-8 is any, its feature exist
In the negative material also includes carbon/silicon composite sol 3-5 parts；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.
10. a kind of LiFePO4-NCM ternary material power lithium-ion batteries as claimed in claim 9, it is characterised in that described
The preparation method of negative material comprises the following steps：
A）Negative pole granular materials, conductive agent, negative electrode binder, carbon/silicon composite sol are uniformly mixed according to a ratio, addition solvent is dilute
2-4 times is released, 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.
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