CN106058262B - A kind of high power lithium ion cell - Google Patents
A kind of high power lithium ion cell Download PDFInfo
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- CN106058262B CN106058262B CN201610365041.XA CN201610365041A CN106058262B CN 106058262 B CN106058262 B CN 106058262B CN 201610365041 A CN201610365041 A CN 201610365041A CN 106058262 B CN106058262 B CN 106058262B
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 a kind of high power lithium ion cell, including positive plate, negative plate, diaphragm and electrolyte, the lithium ion battery includes graphene composite conductive agent, and the high power lithium ion cell is dispersed in positive electrode active materials and negative electrode active material；The mass fraction of the graphene composite conductive agent each component is：120 150 parts of graphenes, 20 35 parts of Super p, 10 15 parts of carbon nanotubes, 30 45 parts of nonylphenol polyoxyethylene ether, 10 25 parts of monoethanolamine, 200 300 parts of solvents, 23 parts of auxiliary agents, 7 10 parts of conducting polymer agent, 24 parts of glass microballoons and 38 parts of acetylacetone,2,4-pentanedione iridium.The present invention using the excellent electric conductivity of graphene, is improved the capacity of electrode material, reduces the internal resistance of cell, improved battery cycle life, save cost so that lithium ion battery is more competitive based on graphene.
Description
Technical field
The present invention relates to lithium ion battery more particularly to a kind of height for reducing cost, improving electric conductivity and cycle life
Power lithium ion cells.
Background technology
Lithium ion battery has many advantages, such as high-energy-density, memory-less effect, obtains people's as new energy again in recent years
Favor, to develop rapidly, with the maturation of technology, requirement of the people to lithium ion battery is also higher and higher.
The lithium ion battery of the prior art mainly uses electrically conductive graphite, acetylene black and carbon nanotube as conductive agent, acetylene
The black chain object being made of amorphous carbon particles spherical in shape is current the most widely used conductive agent, cheap, but
In order to achieve the purpose that contact with each other between enhancing electrode active material, required additive amount is larger, to cause electrode capacity
Decline；Carbon nanotube is the one-dimensional carbonaceous material in line style, and compared with acetylene black, carbon nanotube has more preferably electric conductivity
And the shortcomings that additive amount is few, but carbon nanotube at present is expensive, and there are difficulties in dispersion when being used as conductive agent.
1529382 A of China Patent Publication No. CN, publication date September in 2004 15 days, entitled high power plastics lithium ion
The patent of invention of battery, this application discloses a kind of high-power plastic lithium-ion cells, including positive plate, negative plate, electricity to be situated between
Film material, electrolyte material, soft compound package material and plastic shell, positive plate include positive electrode, adhesive, DBP, carbon
Black, aluminium net, negative plate include negative material, adhesive, DBP, carbon black, copper mesh, and membrane materials for electrolyte includes adhesive, titanium dioxide
Silicon, DBP.Positive plate, negative plate and dielectric film are combined unit battery core by heating, and unit battery core is overlapped, using multiple
After closing membrane material packaging, assembled battery is formed, lug is drawn, the positive and negative electrode of assembled battery is made to pass through ear pole material and positive and negative electrode
Terminal connects, and assembled battery is placed in plastics in vivo, so that lid is passed through ultrasonic wave with box body and merges, form complete high-power modeling
Expect lithium ion battery.Disadvantage is that the prior art in order to prevent high-multiplying power discharge when, at battery pole ear and battery core fever
Measure it is excessive, shorten cycle performance of battery and increase conductive black content, while reducing calorific value, the energy of battery can be reduced
Density；In order to increase the battery high rate cyclic service life, selection increases binder content, will increase the internal resistance of cell, battery-heating amount
Increase.
Invention content
There is provided the purpose of the present invention is to solve the deficiencies in the prior art it is a kind of reduce cost, improve electric conductivity and
The high power lithium ion cell of cycle life.
To achieve the goals above, the present invention uses following technical scheme：
A kind of high power lithium ion cell, including positive plate, negative plate, diaphragm and electrolyte, the positive plate include just
Pole collector and the positive electrode active materials being arranged on the plus plate current-collecting body, the negative plate include negative current collector and set
The negative electrode active material on the negative current collector is set, the lithium ion battery includes graphene composite conductive agent, the Gao Gong
Rate lithium ion battery is dispersed in positive electrode active materials and negative electrode active material；The graphene composite conductive agent each component
Mass fraction be：120-150 parts of graphenes, 20-35 parts of Super-p, 10-15 parts of carbon nanotubes, 30-45 parts of polyoxyethylene nonyl phenyls
Vinethene, 10-25 part monoethanolamine, 200-300 parts of solvents, 2-3 parts of auxiliary agents, 7-10 parts of conducting polymer agent, 2-4 parts of glass are micro-
Pearl and 3-8 parts of acetylacetone,2,4-pentanedione iridium.In the technical scheme, the structure of graphene can be understood as the graphite of single layer, therefore have
Extremely excellent electric conductivity, the movement velocity of wherein electronics have reached the 1/300 of the light velocity, while the unique two-dimensional nano of graphene
Layer structure and huge specific surface area have advantage more outstanding compared to carbon nanotube or carbon black etc. as conductive agent；
And it is then to solve stone to improve the dispersing uniformity of graphene in a solvent to select nonylphenol polyoxyethylene ether and monoethanolamine
The problem of black alkene part difficulties in dispersion；
The selection of glass microballoon, which can make graphene under the influence of a magnetic field, makes it be more easy to disperse, with polyoxyethylene nonyl phenyl second
Alkene ether, monoethanolamine generate collaboration peptizaiton, and graphene dispersion uniformly can make graphene composite conductive agent both play
The advantage of high electron conduction improves the transmission rate of ion, and can play huge specific surface area advantage raising and react
The imbibition liquid-keeping property of active material and its transmittability of lithium ion in journey.
The addition of acetylacetone,2,4-pentanedione iridium is primarily to improve the stability of battery, to improve the security performance of battery.
Preferably, the solvent is one kind in cyclohexanone, cyclopentanone, ethyl alcohol, acetone, hexamethylene or tetrahydrofuran.
Preferably, the conducting polymer agent is polyacetylene, gathers to styrene or polyaniline.
Preferably, graphene be particle diameter distribution in 10 nanometers -100 microns of black powder, be by -1000 layers of phase of single layer
Carbonaceous material parallel or close to parallel graphene sheet layer composition, specific surface area is 50-1500 ㎡/g.
Preferably, auxiliary agent is made of the raw material of following parts by weight：5-10 parts of propylene glycol monostearate, stearic acid polyoxy
15-25 parts of 10-15 parts of vinyl acetate, 5-10 parts of sodium alginate and silane coupling agent.
Preferably, the preparation method of the graphene composite conductive agent includes the following steps：
1) graphene, nonylphenol polyoxyethylene ether are mixed with glass microballoon with the solvent of half, in 55-65 DEG C of ultrasound point
10-25min is dissipated, premixed liquid A is obtained；
2) Super-p, carbon nanotubes, monoethanolamine are mixed with acetylacetone,2,4-pentanedione iridium with remaining solvent, at 78-90 DEG C
30-60min is stirred, premixed liquid B is obtained；
3) the premixed liquid A that step 1) the obtains premixed liquid B obtained with step 2) are stirred and auxiliary agent and conduction is added
Polymeric agent carries out good pressure distribution processing at pressure 21000PSI, then heats to 150-220 DEG C, 3-6h is stirred, after cooling
It is 10-20nm to be ground into grain size, obtains graphene composite conductive agent.
Preferably, step 1) graphene is first added in acetic acid before mixing, 90 DEG C are warming up to, stirs 3h, Zhi Houxi
Only it and dries.
Preferably, supersonic frequency is 50-65KHz.
Beneficial effects of the present invention：
1) present invention using the excellent electric conductivity of graphene, is improved the capacity of electrode material, is reduced electricity based on graphene
Pond internal resistance improves battery cycle life；
2) the graphene composite conductive agent for preparing of the present invention but improves 6-10% preparing lithium ion battery 2C multiplying powers, saves
Cost is saved so that lithium ion battery is more competitive；
3) conductive agent electronic conduction ability produced by the present invention is strong and heat conduction is uniform, is doped to inside lithium ion battery
With stronger imbibition liquid-keeping property.
Specific implementation mode
Technical solution in the embodiment of the present invention is subjected to clear, complete description below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
All other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
Graphene used in the present invention is purchased from Ningbo Mo Xi Science and Technology Ltd.s, remaining raw material is commercially available.Graphite
Alkene is particle diameter distribution in 10 nanometers -100 microns of black powder, is parallel or close to parallel stone by -1000 layers of single layer
The carbonaceous material that black alkene lamella is constituted, specific surface area are 50-1500 ㎡/g.
Embodiment 1
A kind of high power lithium ion cell, including positive plate, negative plate, diaphragm and electrolyte, the positive plate include just
Pole collector and the positive electrode active materials being arranged on the plus plate current-collecting body, the negative plate include negative current collector and set
The negative electrode active material on the negative current collector is set, the lithium ion battery includes graphene composite conductive agent, the Gao Gong
Rate lithium ion battery is dispersed in positive electrode active materials and negative electrode active material；The graphene composite conductive agent each component
Mass fraction be：120 parts of graphenes, 20 parts of Super-p, 10 parts of carbon nanotubes, 30 parts of nonylphenol polyoxyethylene ether, 10 parts of lists
Ethanol amine, 200 parts of solvents, 2 parts of auxiliary agents, 7 parts of conducting polymer agent, 2 parts of glass microballoons and 3 parts of acetylacetone,2,4-pentanedione iridium.
Solvent is cyclohexanone.
Conducting polymer agent is polyacetylene.
Auxiliary agent is made of the raw material of following parts by weight：5 parts of propylene glycol monostearate, 10 parts of polyoxyethylene stearic acid ester,
15 parts of 5 parts of sodium alginate and silane coupling agent.
The preparation method of graphene composite conductive agent includes the following steps：
1) graphene is first added in acetic acid, is warming up to 90 DEG C, stirs 3h, cleans and dries later；By graphene, nonyl
Phenol polyethenoxy ether is mixed with glass microballoon with the solvent of half, in 55 DEG C of ultrasonic disperse 10min, obtains premixed liquid A；Supersonic frequency
Rate is 50KHz；
2) Super-p, carbon nanotubes, monoethanolamine are mixed with acetylacetone,2,4-pentanedione iridium with remaining solvent, is stirred at 78 DEG C
30min is mixed, premixed liquid B is obtained；
3) the premixed liquid A that step 1) the obtains premixed liquid B obtained with step 2) are stirred and auxiliary agent and conduction is added
Polymeric agent carries out good pressure distribution processing at pressure 21000PSI, then heats to 150 DEG C, stirs 3h, is ground into after cooling
Grain size is 10-20nm, obtains graphene composite conductive agent.
Embodiment 2
A kind of high power lithium ion cell, including positive plate, negative plate, diaphragm and electrolyte, the positive plate include just
Pole collector and the positive electrode active materials being arranged on the plus plate current-collecting body, the negative plate include negative current collector and set
The negative electrode active material on the negative current collector is set, the lithium ion battery includes graphene composite conductive agent, the Gao Gong
Rate lithium ion battery is dispersed in positive electrode active materials and negative electrode active material；The graphene composite conductive agent each component
Mass fraction be：130 parts of graphenes, 30 parts of Super-p, 12 parts of carbon nanotubes, 37 parts of nonylphenol polyoxyethylene ether, 18 parts of lists
Ethanol amine, 260 parts of solvents, 3 parts of auxiliary agents, 8 parts of conducting polymer agent, 3 parts of glass microballoons and 7 parts of acetylacetone,2,4-pentanedione iridium.Solvent is second
Alcohol.
Conducting polymer agent is poly- to styrene.
Auxiliary agent is made of the raw material of following parts by weight：7 parts of propylene glycol monostearate, 13 parts of polyoxyethylene stearic acid ester,
18 parts of 8 parts of sodium alginate and silane coupling agent.
The preparation method of graphene composite conductive agent includes the following steps：
1) graphene is first added in acetic acid, is warming up to 90 DEG C, stirs 3h, cleans and dries later；By graphene, nonyl
Phenol polyethenoxy ether is mixed with glass microballoon with the solvent of half, in 60 DEG C of ultrasonic disperse 19min, obtains premixed liquid A；Supersonic frequency
Rate is 60KHz；
2) Super-p, carbon nanotubes, monoethanolamine are mixed with acetylacetone,2,4-pentanedione iridium with remaining solvent, is stirred at 85 DEG C
40min is mixed, premixed liquid B is obtained；
3) the premixed liquid A that step 1) the obtains premixed liquid B obtained with step 2) are stirred and auxiliary agent and conduction is added
Polymeric agent carries out good pressure distribution processing at pressure 21000PSI, then heats to 180 DEG C, stirs 4h, is ground into after cooling
Grain size is 10-20nm, obtains graphene composite conductive agent.
Embodiment 3
A kind of high power lithium ion cell, including positive plate, negative plate, diaphragm and electrolyte, the positive plate include just
Pole collector and the positive electrode active materials being arranged on the plus plate current-collecting body, the negative plate include negative current collector and set
The negative electrode active material on the negative current collector is set, the lithium ion battery includes graphene composite conductive agent, the Gao Gong
Rate lithium ion battery is dispersed in positive electrode active materials and negative electrode active material；The graphene composite conductive agent each component
Mass fraction be：150 parts of graphenes, 35 parts of Super-p, 15 parts of carbon nanotubes, 45 parts of nonylphenol polyoxyethylene ether, 25 parts of lists
Ethanol amine, 300 parts of solvents, 3 parts of auxiliary agents, 10 parts of conducting polymer agent, 4 parts of glass microballoons and 8 parts of acetylacetone,2,4-pentanedione iridium.Solvent is ring
Pentanone.
Conducting polymer agent is polyaniline.
Auxiliary agent is made of the raw material of following parts by weight：10 parts of propylene glycol monostearate, 15 parts of polyoxyethylene stearic acid ester,
25 parts of 10 parts of sodium alginate and silane coupling agent.
The preparation method of graphene composite conductive agent includes the following steps：
1) graphene is first added in acetic acid, is warming up to 90 DEG C, stirs 3h, cleans and dries later；By graphene, nonyl
Phenol polyethenoxy ether is mixed with glass microballoon with the solvent of half, in 65 DEG C of ultrasonic disperse 25min, obtains premixed liquid A；Supersonic frequency
Rate is 65KHz；
2) Super-p, carbon nanotubes, monoethanolamine are mixed with acetylacetone,2,4-pentanedione iridium with remaining solvent, is stirred at 90 DEG C
60min is mixed, premixed liquid B is obtained；
3) the premixed liquid A that step 1) the obtains premixed liquid B obtained with step 2) are stirred and auxiliary agent and conduction is added
Polymeric agent carries out good pressure distribution processing at pressure 21000PSI, then heats to 220 DEG C, stirs 6h, is ground into after cooling
Grain size is 10-20nm, obtains graphene composite conductive agent.
Embodiment 4
A kind of high power lithium ion cell, including positive plate, negative plate, diaphragm and electrolyte, the positive plate include just
Pole collector and the positive electrode active materials being arranged on the plus plate current-collecting body, the negative plate include negative current collector and set
The negative electrode active material on the negative current collector is set, the lithium ion battery includes graphene composite conductive agent, the Gao Gong
Rate lithium ion battery is dispersed in positive electrode active materials and negative electrode active material；The graphene composite conductive agent each component
Mass fraction be：145 parts of graphenes, 30 parts of Super-p, 13 parts of carbon nanotubes, 40 parts of nonylphenol polyoxyethylene ether, 25 parts of lists
Ethanol amine, 300 parts of solvents, 3 parts of auxiliary agents, 10 parts of conducting polymer agent, 5 parts of glass microballoons and 7 parts of acetylacetone,2,4-pentanedione iridium.
Solvent is tetrahydrofuran.
Conducting polymer agent is polyacetylene.
Auxiliary agent is made of the raw material of following parts by weight：9 parts of propylene glycol monostearate, 14 parts of polyoxyethylene stearic acid ester,
23 parts of 7 parts of sodium alginate and silane coupling agent.
The preparation method of graphene composite conductive agent includes the following steps：
1) graphene, nonylphenol polyoxyethylene ether are mixed with glass microballoon with the solvent of half, in 55-65 DEG C of ultrasound point
15min is dissipated, premixed liquid A is obtained；Supersonic frequency is 60KHz；
2) Super-p, carbon nanotubes, monoethanolamine are mixed with acetylacetone,2,4-pentanedione iridium with remaining solvent, at 78-90 DEG C
45min is stirred, premixed liquid B is obtained；
3) the premixed liquid A that step 1) the obtains premixed liquid B obtained with step 2) are stirred and auxiliary agent and conduction is added
Polymeric agent carries out good pressure distribution processing at pressure 21000PSI, then heats to 190 DEG C, stirs 5h, is ground into after cooling
Grain size is 10-20nm, obtains graphene composite conductive agent.
Comparative example 1, using carbon black as conductive agent.
The conductive agent of the graphene composite conductive agent of embodiment 1-4 and comparative example 1 is fabricated to flexible packing lithium ion
Battery carries out cycle performance test, as a result as follows：
Table 1, test result
| Specific capacity (mAh/g) | First charge discharge efficiency (%) | Capacity retention ratio (%) after 100 cycles | |
| Embodiment 1 | 600 | 85 | 91 |
| Embodiment 2 | 720 | 81 | 87 |
| Embodiment 3 | 866 | 78 | 89 |
| Embodiment 4 | 740 | 79 | 88 |
| Comparative example 1 | 460 | 66 | 51 |
The present invention improves the capacity of electrode material using graphene composite conductive agent using the excellent electric conductivity of graphene,
The internal resistance of cell is reduced, battery cycle life is improved；2C multiplying powers but improve 6-10%, save cost so that lithium ion battery
It is more competitive.
It should be understood that those skilled in the art, can be improved or be become according to the above description
It changes, and all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (7)
1. a kind of high power lithium ion cell, including positive plate, negative plate, diaphragm and electrolyte, the positive plate includes anode
Collector and the positive electrode active materials being arranged on the plus plate current-collecting body, the negative plate include negative current collector and setting
Negative electrode active material on the negative current collector, which is characterized in that the lithium ion battery includes graphene composite conductive agent,
The graphene composite conductive agent is dispersed in positive electrode active materials and negative electrode active material；The graphene composite conductive
The mass fraction of agent each component is：120-150 parts of graphenes, 20-35 parts of Super-p, 10-15 parts of carbon nanotubes, 30-45 parts of nonyls
Base phenol polyethenoxy ether, 10-25 part monoethanolamine, 200-300 parts of solvents, 2-3 parts of auxiliary agents, 7-10 parts of conducting polymer agent, 2-4
Part glass microballoon and 3-8 parts of acetylacetone,2,4-pentanedione iridium；
The preparation method of the graphene composite conductive agent includes the following steps：
1）Graphene, nonylphenol polyoxyethylene ether are mixed with glass microballoon with the solvent of half, in 55-65 DEG C of ultrasonic disperse
10-25min obtains premixed liquid A；
2）Super-p, carbon nanotubes, monoethanolamine are mixed with acetylacetone,2,4-pentanedione iridium with remaining solvent, stirred at 78-90 DEG C
30-60min obtains premixed liquid B；
3）By step 1）Obtained premixed liquid A and step 2）Obtained premixed liquid B is stirred and auxiliary agent and conductive polymer is added
Sub- agent carries out good pressure distribution processing at pressure 21000PSI, then heats to 150-220 DEG C, stirs 3-6h, is ground after cooling
It is 10-20nm at grain size, obtains graphene composite conductive agent.
2. a kind of high power lithium ion cell according to claim 1, which is characterized in that the solvent is cyclohexanone, ring
One kind in pentanone, ethyl alcohol, acetone, hexamethylene or tetrahydrofuran.
3. a kind of high power lithium ion cell according to claim 1, which is characterized in that the conducting polymer agent is poly-
Acetylene gathers to styrene or polyaniline.
4. a kind of high power lithium ion cell according to claim 1 or 2 or 3, which is characterized in that graphene is grain size point
It is distributed in 10 nanometers -100 microns of black powder, is parallel or close to parallel graphene sheet layer structure by -1000 layers of single layer
At carbonaceous material, specific surface area be 50-1500 ㎡/g.
5. a kind of high power lithium ion cell according to claim 1 or 2 or 3, which is characterized in that auxiliary agent is by following weight
The raw material composition of part：5-10 parts of propylene glycol monostearate, 10-15 parts of polyoxyethylene stearic acid ester, 5-10 parts of sodium alginate with
15-25 parts of silane coupling agent.
6. a kind of high power lithium ion cell according to claim 1, which is characterized in that step 1）Graphene is before mixing
It is first added in acetic acid, is warming up to 90 DEG C, stir 3h, clean and dry later.
7. a kind of high power lithium ion cell according to claim 1, which is characterized in that supersonic frequency 50-65KHz.
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| CN114479713A (en) * | 2022-02-28 | 2022-05-13 | 江苏鑫华半导体科技股份有限公司 | Composite conductive adhesive and preparation method and application thereof |
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| JP6988169B2 (en) * | 2017-05-26 | 2022-01-05 | トヨタ自動車株式会社 | A method for manufacturing a negative electrode for a non-aqueous electrolyte secondary battery, and a method for manufacturing a non-aqueous electrolyte secondary battery. |
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