CN107749476A - A kind of LiMn2O4 power lithium-ion battery - Google Patents
A kind of LiMn2O4 power lithium-ion battery Download PDFInfo
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- CN107749476A CN107749476A CN201610910805.9A CN201610910805A CN107749476A CN 107749476 A CN107749476 A CN 107749476A CN 201610910805 A CN201610910805 A CN 201610910805A CN 107749476 A CN107749476 A CN 107749476A
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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
- H01M4/36—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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- 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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—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
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- 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 LiMn2O4 power lithium-ion battery, including positive pole and negative pole, and positive electrode includes 90 94 parts of LiMn2O4,2.5 3.5 parts of positive conductive agent, 1.5 2.5 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.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 LiMn2O4 power lithium-ion battery.
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. 201310234941.7 discloses a kind of lithium ion battery and its LiMn2O4
Positive electrode, the manganate cathode material for lithium are nanometer time LiMn2O4, the nanometer time LiMn2O4 with manganese acetate, sodium peroxydisulfate and
Manganese nitrate is ball shaped nano made from raw material time lithium manganate particle, and the particle diameter of the nanometer time lithium manganate particle is received for 100-112
Rice.Compared to prior art, the manganate cathode material for lithium of the invention can improve the capacity of lithium ion battery, improve it and follow
Ring performance and charge-discharge performance.
But the lithium manganese oxide lithium-ion power battery of prior art there is also it is certain the defects of, for example, negative material is universal
Elect graphite as, the cooperation of manganate cathode material for lithium and negative material is not ideal enough；In addition negative material particle is big, negative material exists
The problem of adhesive force and poor uniformity on copper foil, and then the internal resistance of cell can be caused higher, cryogenic property, high temperature discharge
Can, 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 LiMn2O4 power lithium-ion battery.The present invention selects
LiMn2O4 is as positive active material, from special hud typed carbon material as negative material, positive electrode and negative material
Work good；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.It is fabricated to
After 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.
The present invention concrete technical scheme be：A kind of LiMn2O4 power lithium-ion battery, including positive pole and negative pole, it is described just
Pole includes plus plate current-collecting body and positive electrode, and the negative pole includes negative current collector and negative material；By weight, it is described just
Pole material includes LiMn2O4 90-94 parts, positive conductive agent 2.5-3.5 parts, positive electrode binder 1.5-2.5 parts, lytic agent 15-25
Part.
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 from LiMn2O4 as positive active material, from special hud typed carbon material as negative material,
Positive electrode 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,
It is low to contact internal resistance.After being fabricated to lithium ion battery, the internal resistance of cell is not only reduced, and the cryogenic property of battery, height can also be improved
Warm nature energy 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 is 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 LiMn2O4 as positive active material, choosing
Worked good by the use of special hud typed carbon material as negative material, positive electrode with negative material；And negative material particle is small, bear
Adhesive force and uniformity of the pole material on copper foil are good, and contact internal resistance is low.After being fabricated to lithium ion battery, not only reduce in battery
Resistance, 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 LiMn2O4 power lithium-ion battery, 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 LiMn2O4,3 parts of positive conductive agent, 2 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；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 LiMn2O4 power lithium-ion battery, 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 LiMn2O4,3 parts of positive conductive agent, 2 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 LiMn2O4 power lithium-ion battery, 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 90 parts of LiMn2O4,2.5 parts of positive conductive agent, 1.5 parts of positive electrode binder, lytic agent 15
Part.
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 LiMn2O4 power lithium-ion battery, 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 LiMn2O4,35 parts of positive conductive agent, 2.5 parts of positive electrode binder, lytic agent 25
Part.
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, embodiment 2, using negative material as conventional artificial's graphite, just
Pole material is that two kinds of lithium-ion-power cells of LiMn2O4 are comparative example 1, comparative example 2, carries out performance test.
1st, high-temperature behavior compares：High-temperature behavior test, test result are carried out to embodiment 1-2, comparative example 1-2 at 55 DEG C
For：
The battery capacity conservation rate of embodiment 1 is 96.02%,
The battery capacity conservation rate of embodiment 2 is 96.51%,
The battery capacity conservation rate of comparative example 1 is 93.89%,
The battery capacity conservation rate of comparative example 2 is 94.52%.
The capacity restoration rate of embodiment 1 is 97.06%,
The capacity resuming rate of embodiment 2 is 97.44%,
The capacity resuming rate of comparative example 1 is 95.81%,
The capacity resuming rate of comparative example 2 is 95.96%.
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 LiMn2O4 power lithium-ion battery, including positive pole and negative pole, the positive pole includes plus plate current-collecting body and positive pole material
Material, the negative pole include negative current collector and negative material；It is characterized in that：By weight, the positive electrode includes manganese
Sour lithium 90-94 parts, positive conductive agent 2.5-3.5 parts, positive electrode binder 1.5-2.5 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 LiMn2O4 power lithium-ion battery as claimed in claim 1, it is characterised in that the negative pole granular materials
Particle diameter is d50≤6μm。
3. a kind of LiMn2O4 power lithium-ion battery as claimed in claim 1, it is characterised in that the negative electrode binder is by matter
Amount is than being 1:1-2 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein the butadiene-styrene rubber is the benzene that particle diameter is less than 0.2 μm
Ethylene copolymer, the pH values of butadiene-styrene rubber are 6.5-7.5.
4. a kind of LiMn2O4 power lithium-ion battery as claimed in claim 1, it is characterised in that the negative pole granular materials
Preparation method 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. LiMn2O4 power lithium-ion battery as claimed in claim 1, it is characterised in that step 3）In, at graphitization
The reason time is 5h.
A kind of 6. LiMn2O4 power lithium-ion battery as claimed in claim 1, it is characterised in that step 4）In, Delanium
It 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, and thermostatic hold-time is
24h。
A kind of 7. LiMn2O4 power lithium-ion battery as claimed in claim 1, it is characterised in that step 4）In, the polymerization
Thing precursor solution is Water-soluble phenolic resin solution.
A kind of 8. LiMn2O4 power lithium-ion battery as described in claim 1-7 is any, it is characterised in that the negative material
Also include carbon/silicon composite sol 3-5 parts.
A kind of 9. LiMn2O4 power lithium-ion battery as claimed in claim 8, it is characterised in that the system of the carbon/Ludox
Preparation Method 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.
A kind of 10. LiMn2O4 power lithium-ion battery as claimed in claim 8, it is characterised in that the preparation of the negative material
Method 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.
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| CN112531160A (en) * | 2019-09-19 | 2021-03-19 | 贝特瑞新材料集团股份有限公司 | Amorphous carbon negative electrode material and preparation method and application thereof |
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