CN108711613A - A kind of complex ternary positive electrode that polyaniline/polyethylene glycol wraps up altogether and its preparation and application - Google Patents

A kind of complex ternary positive electrode that polyaniline/polyethylene glycol wraps up altogether and its preparation and application Download PDF

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CN108711613A
CN108711613A CN201810480195.2A CN201810480195A CN108711613A CN 108711613 A CN108711613 A CN 108711613A CN 201810480195 A CN201810480195 A CN 201810480195A CN 108711613 A CN108711613 A CN 108711613A
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polyethylene glycol
polyaniline
positive electrode
wraps
altogether
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胡国荣
亓先跃
杜柯
彭忠东
曹雁冰
王勇
胡凯华
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Central South University
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Abstract

The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to a kind of complex ternary positive electrode that polyaniline/polyethylene glycol wraps up altogether, including positive ternary material and the polyaniline and polyethylene glycol that are coated on its surface.The present invention also provides the preparation method and application of the anode composite ternary material.Complex ternary positive electrode of the present invention, by the surface action between the positive ternary material and the polyaniline and polyethylene glycol, collaboration promotes the electric property of obtained complex ternary positive electrode, improves covered effect and chemical stability.In addition, the present invention innovatively uses wet method method for coating, and it is simple for process, coordinate the component to cooperate with, can further improve covered effect, promote the performance of material, also there are easy to operate, the advantages such as consistency height.

Description

A kind of complex ternary positive electrode that polyaniline/polyethylene glycol wraps up altogether and its preparation And application
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of dual conducting polymer wraps up lithium-ion electric altogether The surface modifying method of pond anode ternary material.
Background technology
Lithium ion battery is widely used in the even large-scale energy storage device of portable electronic product, electric vehicle tool, when The anode material of lithium battery of preceding commercialization mainly has cobalt acid lithium, LiMn2O4, LiFePO4, ternary material etc..Wherein ternary material has The performance for having higher specific capacity high and stable with energy density and power density, operating voltage, to as business anode The active material of research.However the cycle performance of ternary material and high rate performance are poor, while ternary material surface residual alkali content It crosses a height of its and brings many negative effects, such as increase irreversible capacity loss, deteriorate cycle performance, increase processing, storage With the cost of transport.
A kind of mode for improving material electrochemical performance is that surface is modified, this is also in battery material modification using most One of mode.For ternary material, the coating of one layer of nano thickness is coated in material surface, on the one hand can be completely cut off outer Boundary's environment is in direct contact generation side reaction with positive electrode, improves the storge quality of material, still further aspect can also injected After electrolyte and during charge discharge, protect positive electrode from the erosion of ingredient in electrolyte, to have Effect inhibits structure of the material in charge and discharge process to destroy.Common cladding substance is nonconducting insulating compound or is only One kind of ion conductor and electronic conductor, and existing method for coating is not readily available uniform clad with cladding substance, Covered effect is barely satisfactory.
Currently, conducting polymer composite material can be used as anakinetomer for researching and developing electrode material, has researcher Research is modified to anode material for lithium-ion batteries using conducting polymer, as Chinese patent CN104466135A discloses one The method of kind conducting polymer cladding nickel-cobalt lithium manganate cathode material, the patent prepare LiNi by mechanical activation first1/3Co1/ 3Mn1/3Presoma mixed liquor, be added into the presoma mixed liquor polypyrrole aqueous solution or organic solution after to carry out spraying dry Precursor powder that is dry, being uniformly mixed, is finally calcined at 500-700 DEG C, obtains the LiNi of polypyrrole cladding1/3Co1/ 3Mn1/3Positive electrode.The patent improves LiNi1/3Co1/3Mn1/3The cycle performance and capacitance conservation rate of battery.But it is wrapped While covering conducting polymer raising electron conduction, the lithium ion conductive of material is reduced；And its calcination temperature is higher, Polypyrrole can decompose, and influence covered effect.Chinese patent CN107742712A discloses a kind of conducting polymer cladding and mixes The method of miscellaneous type anode material for lithium-ion batteries, the patent obtain doping type positive electrode sample by ball-milling method first, then The material is placed in surfactant, oxidant, conducting polymer composite such as polythiophene in closed container and reacts a period of time, Obtain the lithium ion anode material of conducting polymer cladding.The cation that the patent effectively inhibits nickel-rich positive pole material is mixed Phenomenon is arranged, interface stability is improved.But it coats that process agents useful for same is more, and reaction condition is not easy to control, consistency compared with Difference；And its whole preparation method is more complicated, is unfavorable for industrialized production.Chinese patent CN102723491A discloses one kind The lithium-ion battery composite-electrode material and preparation method thereof of conducting-polymer dipped cladding, the patent is by lithium ion anode or bears Pole material is dipped into the polystyrolsulfon acid organic solution containing the poly- 3,4-ethylene dioxythiophene of eigenstate, after filtration drying i.e. Obtain the anion doped poly- 3,4- ethylenedioxy thiophenes/electrode material composite material of polystyrolsulfon acid root.The patent improves electricity The electric conductivity of pole material improves the chemical property of electrode material.But the patent is using the poly- 3,4- ethylenes of eigenstate Dioxy thiophene, electric conductivity is very poor, and not molten insoluble, subsequently needs to be doped using polystyrolsulfon acid root anion and carries Its high performance, however poly- 3,4-ethylene dioxythiophene is directly added in polystyrolsulfon acid organic solution and can cause by this patent It adulterates the big heavy discount of effect, thereby reduces subsequent covering property；And polystyrolsulfon acid solution has certain acid Property, certain corrosion can be caused to electrode material, to influence material property.
Invention content
For the deficiency and defect mentioned in background above technology, such as the single cladding of conducting polymer, cladding difficulty is big, wraps The defects of coating is uneven, material ions conductivity declines after cladding, that the purpose of the present invention is to provide a kind of covered effects is good, The complex ternary positive electrode that the good polyaniline/polyethylene glycol of chemical stability wraps up altogether.
Second purpose of the invention is, provides the complex ternary that polyaniline/polyethylene glycol described in a kind of offer wraps up altogether A kind of preparation method (that is to say wet-process modified method of tertiary cathode material) of positive electrode.
Third purpose of the present invention is, provides the application of the complex ternary positive electrode.
A kind of complex ternary positive electrode that polyaniline/polyethylene glycol wraps up altogether, including positive ternary material and cladding Polyaniline and polyethylene glycol on its surface.
Complex ternary positive electrode of the present invention by the positive ternary material and the polyaniline and gathers Surface action between ethylene glycol, collaboration promote the obtained electric property of complex ternary positive electrode, improve covered effect and Chemical stability.
Preferably, the positive ternary material is LiNixCoyMn1-x-yO2, wherein 0<=x, y<=1.
Further preferably, positive ternary material is LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2Or LiNi0.8Co0.1Mn0.1O2。
Polyaniline has the structure of class nano wire, and polyethylene glycol and positive ternary material interaction, can cooperate with Achieve the effect that equably to carry out coating modification to ternary material；Additionally aiding improves the mechanical stability of material.
Preferably, the polyaniline is protonic acid doping type.
Preferably, the molecular weight polyethylene glycol ranging from 800 or more；Preferably 1000-4000.Preferred proton The mutual synergistic effect of the polyethylene glycol of acid doping type and preferred molecular weight and positive ternary material is more excellent.
The quality of cladding substance has a certain impact to covered effect, coats the quality of substance and excessively high can change covering material Structure, it is too low, cannot completely or uniformly coat.Preferably, polyaniline is the complex ternary with polyethylene glycol total weight 1~10wt% of the weight of positive electrode；Further preferably 4~6wt%.
The mass ratio of the polyethylene glycol and polyaniline is 1:1~5；Further preferably 1:2~3.It is preferred at this Under ratio, the ionic conductivity of mixed polymer is optimal with electronic conductivity, and covered effect is best.
The present invention also provides a kind of preparations for the complex ternary positive electrode that the polyaniline/polyethylene glycol wraps up altogether Method includes the following steps：
Step (1)：Polyaniline and polyethylene glycol are scattered in organic solvent, dispersion liquid is stirred to get；
Step (2)：Positive ternary material is added into dispersion liquid, dried after being stirred to react to get.
Conductive polymer polyanaline and polyethylene glycol are scattered in organic solvent, stirring in water bath for a period of time, is divided Dispersion liquid；It is slowly added to ternary material into dispersion liquid, reacts certain time, is dried in vacuo and obtains after suction filtration.Based on tertiary cathode The collaboration of material surface activity and the polyethylene glycol and polyaniline, can overcoming cladding, difficulty is big, clad is uneven The technical issues of being difficult to solve in the industries such as material ions conductivity decline after even, cladding；It is good to help to obtain covered effect, changes Learn the good anode composite ternary material of stability.The polymer of the material can be assisted by the surface action with tertiary cathode material With electronic conductivity and ionic conductivity and stress ability to bear is promoted, make to transmit between electrode and electrolyte electronics and " highway " of lithium ion, electric conductivity and the alleviation charge and discharge of ternary material can be increased by carrying out surface modification using the polymer Structure change in electric process can effectively optimize interfacial electrochemistry reaction environment, improve the appearance irreversible for the first time of ternary material Amount, cyclical stability and thermal stability.
The present invention innovatively uses wet method method for coating, simple for process, coordinates the component to cooperate with, can further improve Covered effect promotes the performance of material.
The preparation method, the organic solvent are one or more of N-Methyl pyrrolidone and dimethylbenzene. Preferably, in dispersion liquid, including a concentration of 5~20g/mL that polyaniline is total with the polymer including polyethylene glycol；Further Preferably 10~15g/mL.
Preferably, in step (1), 5~20min is stirred at being 40~80 DEG C in temperature；Preferred temperature is 50~70 ℃。
Preferably, it is 10~30min that step (2), which is stirred to react the time,；
Preferably, drying mode is vacuum drying, vacuum drying temperature is 80~120 DEG C；Further preferably 100 ~110 DEG C.
The present invention also provides a kind of applications of the complex ternary positive electrode, are used as positive electrode active materials, are used for Prepare the anode of lithium ion battery；
Preferably, by anode obtained for being assembled into lithium ion battery.
Compared with prior art, advantage of the invention is that：
The present invention prepares polyaniline by liquid phase method and is modified positive ternary material with polyethylene glycol surface.Polyaniline has class The structure of nano wire equably can carry out coating modification to ternary material；Dual conduction by polyaniline and polyethylene glycol is poly- " highway " of transmission electronics and lithium ion between electrode and electrolyte, and the support of polyethylene glycol can be used as by closing object Effect can significantly improve the mechanical stability of dual polymer.Carrying out surface modification to ternary material using conducting polymer can To avoid being in direct contact for electrolyte and positive active material, inhibit irreversible side reaction, reduces ternary material surface residual alkali and contain Amount improves the aerial stability of material.The dual conducting polymer of polyaniline and polyethylene glycol composition has good electricity Electron conductivity and ionic conductivity and stress ability to bear, three can be increased by carrying out surface modification using the dual polymer The electric conductivity of first material and the structure change in alleviation charge and discharge process, can effectively optimize interfacial electrochemistry reaction environment, change Irreversible capacity for the first time, cyclical stability and the thermal stability of kind ternary material.Preparation process of the present invention is simple, easy to operate, Consistency is high, and the chemical property of positive ternary material significantly improves.
Description of the drawings
Fig. 1 is that polyaniline-polyethylene glycol surface that embodiment 1 obtains is modified LiNi0.8Co0.1Mn0.1O2Composite material is swept Retouch electron microscope.
Fig. 2 is polyaniline, polyethylene glycol, dual polymer, the LiNi that embodiment 1 obtains0.8Co0.1Mn0.1O2And polyphenyl Amine-polyethylene glycol surface is modified LiNi0.8Co0.1Mn0.1O2The infrared spectrogram of composite material.
Fig. 3 is the LiNi of embodiment 1 before modified0.8Co0.1Mn0.1O2Ternary material and polyaniline-polyethylene glycol surface change The LiNi of property0.8Co0.1Mn0.1O2Cycle of the composite material under 1C current densities, in 25 DEG C and 2.8~4.3V voltage ranges is bent Line chart.
Fig. 4 is the LiNi before modified of embodiment 10.8Co0.1Mn0.1O2Ternary material and polyaniline-polyethylene glycol surface are modified LiNi0.8Co0.1Mn0.1O2Cyclic curve of the composite material under 1C current densities, in 55 DEG C and 2.8~4.3V voltage ranges Figure.
Fig. 5 is the LiNi before modified of embodiment 20.6Co0.2Mn0.2O2Ternary material and polyaniline-polyethylene glycol surface are modified LiNi0.6Co0.2Mn0.2O2Cyclic curve of the composite material under 1C current densities, in 25 DEG C and 2.8~4.3V voltage ranges Figure.
Fig. 6 is the LiNi before modified of embodiment 30.5Co0.2Mn0.3O2Ternary material and polyaniline-polyethylene glycol surface are modified LiNi0.6Co0.2Mn0.2O2Cyclic curve of the composite material under 1C current densities, in 25 DEG C and 2.8~4.3V voltage ranges Figure.
Fig. 7 is the LiNi of comparative example 1 before modified0.8Co0.1Mn0.1O2Ternary material is modified with polyaniline surface LiNi0.8Co0.1Mn0.1O2And the LiNi that polyaniline-polyethylene glycol surface is modified0.8Co0.1Mn0.1O2Composite material is in 1C electric currents Cyclic curve figure under density, in 25 DEG C and 2.8~4.3V voltage ranges.
Fig. 8 is the LiNi of comparative example 2 before modified0.6Co0.2Mn0.2O2Ternary material is modified with polyethylene glycol surface LiNi0.6Co0.2Mn0.2O2And the LiNi that polyaniline-polyethylene glycol surface is modified0.6Co0.2Mn0.2O2Composite material is in 1C electric currents Cyclic curve figure under density, in 25 DEG C and 2.8~4.3V voltage ranges.
Specific implementation mode
Following embodiment is intended to illustrate invention rather than limitation of the invention further.
Embodiment 1：
By conductive polymer polyanaline (5612-44-2, doped hydrochloride, the good grain husk in Shandong) and polyethylene glycol (1000Mw, Shanghai Traditional Chinese medicines) with 1:1 mass ratio is scattered in (1 in N-Methyl pyrrolidone solvent:10) 10min, is stirred under 50 DEG C of water-baths, is divided Dispersion liquid；LiNi is slowly added into dispersion liquid0.8Co0.1Mn0.1O2Ternary material, reaction 15min or so, after suction filtration at 100 DEG C It is dried in vacuo to get the LiNi being modified to polyaniline-polyethylene glycol surface0.8Co0.1Mn0.1O2Composite material, wherein polymer Covering amount is 5wt%.
Fig. 1 is the scanning electron microscope (SEM) photograph of rear ternary material before modified.As seen from Figure 1, modified material morphology does not have substantially It changes, is spherical particle, illustrate that cladding process will not damage the whole pattern of material；It can be seen from the figure that cladding The primary particle corner angle of preceding material surface are clearly demarcated, can be evident that material surface has wrapped up thin film, says after cladding It is bright to deposited one layer of coating really in material surface, from the presence for also having film between low range it can be seen from the figure that particle, Illustrate that the film has certain continuity.
Fig. 2 is polyaniline, polyethylene glycol, polymer, LiNi0.8Co0.1Mn0.1O2And polymer surface modification LiNi0.8Co0.1Mn0.1O2The infrared spectrogram of composite material.As seen from Figure 3,3423cm-1The characteristic peaks at place are corresponding It is OH in polyethylene glycol-Stretching vibration；2912cm-1The corresponding characteristic peaks at place are-CH in polyethylene glycol2Symmetrical stretch Contracting vibration；1486cm-1The corresponding characteristic peaks at place are-CH in polyethylene glycol2Bending vibration；1593cm-1The characteristic peak at place It is quinone ring C=N stretching vibrations in polyaniline to be worth corresponding；1124cm-1The corresponding characteristic peaks at place are quinone ring faces in polyaniline Interior C-H bending vibrations.It can thus be appreciated that the clad on ternary material surface is the polymer of polyaniline and polyethylene glycol.
Fig. 3 be before modified after under positive ternary material 1C current densities, 25 DEG C with the cycle in 2.8~4.3V voltage ranges Curve graph.From the figure 3, it may be seen that after unmodified material circulation 100 encloses, the capacity of material is from 181.6mAhg-1It decays to 151.8mAh·g-1, capacity retention ratio 83.6%, and after modified material circulation 100 encloses, the capacity of material from 188.6mAh·g-1Decay to 174.2mAhg-1, capacity retention ratio 92.4%, hence it is evident that higher than unmodified.
Fig. 4 be before modified after under positive ternary material 1C current densities, 55 DEG C with the cycle in 2.8~4.3V voltage ranges Curve graph.As shown in Figure 4, after modified material recycles 100 times at 1C, the capacity of material is from 205.5mAhg-1It decays to 167.3mAh·g-1, capacity retention ratio 81.4%, and the discharge capacity of unmodified material is from 197.1mAhg-1Rapid decaying To 105.6mAhg-1, capacity retention ratio only has 53.6%.
Embodiment 2：
By conductive polymer polyanaline (5612-44-2, sulfuric acid doping, the good grain husk in Shandong) and polyethylene glycol (2000Mw, Shanghai Traditional Chinese medicines) with 2:1 mass ratio is scattered in xylene solvent (1:15) 15min, is stirred under 60 DEG C of water-baths, obtains dispersion liquid；To LiNi is slowly added in dispersion liquid0.6Co0.2Mn0.2O2Ternary material, reaction 20min or so, vacuum is dry at 110 DEG C after suction filtration It is dry to get the LiNi being modified to polyaniline-polyethylene glycol surface0.6Co0.2Mn0.2O2Composite material, the wherein covering amount of polymer For 4wt%.
Fig. 5 be before modified after under positive ternary material 1C current densities, 25 DEG C with the cycle in 2.8~4.3V voltage ranges Curve graph, as shown in Figure 5, after material before modified recycles 100 times at 1C, the capacity of material is from 172.7mAhg-1It declines rapidly Reduce to 145.4mAhg-1, capacity retention ratio is only 84.2%, and 100 discharge capacities of modified material circulation from 177.5mAh·g-1Decay to 162.6mAhg-1, capacity retention ratio 91.6%.
Embodiment 3：
By conductive polymer polyanaline (5612-44-2, bigcatkin willow acid doping, the good grain husk in Shandong) and polyethylene glycol (3000Mw, on Extra large traditional Chinese medicines) with 3:1 mass ratio is scattered in xylene solvent (1:20) 15min, is stirred under 70 DEG C of water-baths, obtains dispersion liquid； LiNi is slowly added into dispersion liquid0.5Co0.2Mn0.3O2Ternary material, reaction 25min or so, vacuum is dry at 90 DEG C after suction filtration It is dry to get the LiNi being modified to polyaniline-polyethylene glycol surface0.5Co0.2Mn0.3O2Composite material, the wherein covering amount of polymer For 6wt%.
Fig. 6 be before modified after under positive ternary material 1C current densities, 25 DEG C with the cycle in 2.8~4.3V voltage ranges Curve graph, it will be appreciated from fig. 6 that after material before modified recycles 100 times at 1C, the capacity of material is from 159.7mAhg-1It declines rapidly Reduce to 130.5mAhg-1, capacity retention ratio is only 81.7%, and 100 discharge capacities of modified material circulation from 164.5mAh·g-1Decay to 151.7mAhg-1, capacity retention ratio 92.2%.
Comparative example 1：
Compared with Example 1, difference lies in polyaniline-polyethylene glycol conducting polymer is changed to layer/polyaniline conductive polymer.
Fig. 7 be before modified after under positive ternary material 1C current densities, 25 DEG C with the cycle in 2.8~4.3V voltage ranges Curve graph.As shown in Figure 7, from 181.6mAhg after the capacity of unmodified material recycles 100 weeks at 1C-1It decays to 151.8mAh·g-1, capacity retention ratio only has 83.6%, and it is polyaniline-modified after material capacity from 185.4mAhg-1Decaying To 164.5mAhg-1, capacity retention ratio 88.7%, the capacity of the poly ethyldiol modified material of polyaniline-is from 188.6mAhg-1Decay to 174.2mAhg-1, capacity retention ratio 92.4%.
Comparative example 2：
Compared with Example 2, difference lies in polyaniline-polyethylene glycol conducting polymer is changed to polyethylene glycol conducting polymer Object.
Fig. 8 be before modified after under positive ternary material 1C current densities, 25 DEG C with the cycle in 2.8~4.3V voltage ranges Curve graph.As shown in Figure 8, from 172.7mAhg after the capacity of unmodified material recycles 100 weeks at 1C-1It decays to rapidly 145.4mAh·g-1, capacity retention ratio is only 84.2%, and it is poly ethyldiol modified after material capacity from 174.8mAhg-1It declines Reduce to 153.7mAhg-1, capacity retention ratio 87.9%, the capacity of the poly ethyldiol modified material of polyaniline-is from 177.5mAh g-1Decay to 162.6mAhg-1, capacity retention ratio 91.6%.

Claims (10)

1. a kind of complex ternary positive electrode that polyaniline/polyethylene glycol wraps up altogether, which is characterized in that including positive ternary material And it is coated on the polyaniline and polyethylene glycol on its surface.
2. the complex ternary positive electrode that polyaniline/polyethylene glycol as described in claim 1 wraps up altogether, which is characterized in that institute The positive ternary material stated is LiNixCoyMn1-x-yO2, wherein 0<=x, y<=1.
3. the complex ternary positive electrode that polyaniline/polyethylene glycol as described in claim 1 wraps up altogether, which is characterized in that institute The polyaniline stated is protonic acid doping type.
4. the complex ternary positive electrode that polyaniline/polyethylene glycol as described in claim 1 wraps up altogether, which is characterized in that institute The molecular weight polyethylene glycol stated ranging from 800 or more.
5. the complex ternary positive electrode that polyaniline/polyethylene glycol as described in claim 1 wraps up altogether, which is characterized in that poly- 1~10wt% of aniline and the weight that polyethylene glycol total weight is the complex ternary positive electrode.
6. the complex ternary positive electrode that polyaniline/polyethylene glycol as described in claim 1 wraps up altogether, which is characterized in that institute The mass ratio of the polyethylene glycol and polyaniline stated is 1:1~5.
7. a kind of system for the complex ternary positive electrode that claim 1~6 any one of them polyaniline/polyethylene glycol wraps up altogether Preparation Method, which is characterized in that include the following steps：
Step (1)：Polyaniline and polyethylene glycol are scattered in organic solvent, dispersion liquid is stirred to get；
Step (2)：Positive ternary material is added into dispersion liquid, dried after being stirred to react to get.
8. preparation method as claimed in claim 7, which is characterized in that the organic solvent is N-Methyl pyrrolidone and two One or more of toluene；
In dispersion liquid, including a concentration of 5~20g/mL that polyaniline is total with the polymer including polyethylene glycol.
9. preparation method as claimed in claim 7, which is characterized in that in step (1), 5 are stirred at being 40~80 DEG C in temperature ~20min；
Step (2) is stirred to react the time as 10~30min；
Drying mode is vacuum drying, and vacuum drying temperature is 80~120 DEG C.
10. described in a kind of claim 1~6 any one of them complex ternary positive electrode or any one of claim 7~9 The application of complex ternary positive electrode made from preparation method, which is characterized in that be used as positive electrode active materials, be used to prepare lithium from The anode of sub- battery；
Preferably, by anode obtained for being assembled into lithium ion battery.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109244430A (en) * 2018-11-13 2019-01-18 武汉科技大学 Polymer and nitrogen-doped carbon nanometer pipe are modified nickel cobalt manganese anode material and preparation method thereof altogether
CN110061234A (en) * 2019-05-27 2019-07-26 河南科技学院 A kind of anode material for lithium-ion batteries and preparation method thereof
CN112201791A (en) * 2020-10-23 2021-01-08 江苏大学 Method for improving ternary cathode material of lithium ion battery by oxygen-absorbing self-healing film
CN112563504A (en) * 2020-12-09 2021-03-26 北京理工大学重庆创新中心 Method for regulating and controlling surface transmission efficiency of lithium battery anode material and obtained anode material
CN114937766A (en) * 2022-05-31 2022-08-23 济宁学院 Preparation method of transition metal doped poly (m-phenylenediamine) -coated positive electrode material
WO2024016467A1 (en) * 2022-07-20 2024-01-25 广东邦普循环科技有限公司 Preparation method for polymer/lithium nickel manganese oxide composite material, and product and use thereof
WO2024021273A1 (en) * 2022-07-27 2024-02-01 广东邦普循环科技有限公司 High-voltage ternary positive electrode material and preparation method therefor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130168611A1 (en) * 2010-10-27 2013-07-04 Ocean's King Lighting Science & Technology Co., Ltd., Composite electrode material, manufacturing method and application thereof
CN103682311A (en) * 2013-12-04 2014-03-26 浙江大学 Preparation method of ternary composite cathode material of lithium ion battery
CN106803574A (en) * 2016-12-26 2017-06-06 宁波中车新能源科技有限公司 Anode material for lithium-ion batteries and its preparation method and application
CN107293713A (en) * 2017-06-19 2017-10-24 中国科学院长春应用化学研究所 A kind of super-low-temperature lithium-ion cell composite positive pole and preparation method thereof
CN107732220A (en) * 2017-11-27 2018-02-23 中南大学 The preparation method of the ternary cathode material of lithium ion battery of the mesoporous carbon coating of N doping

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130168611A1 (en) * 2010-10-27 2013-07-04 Ocean's King Lighting Science & Technology Co., Ltd., Composite electrode material, manufacturing method and application thereof
CN103682311A (en) * 2013-12-04 2014-03-26 浙江大学 Preparation method of ternary composite cathode material of lithium ion battery
CN106803574A (en) * 2016-12-26 2017-06-06 宁波中车新能源科技有限公司 Anode material for lithium-ion batteries and its preparation method and application
CN107293713A (en) * 2017-06-19 2017-10-24 中国科学院长春应用化学研究所 A kind of super-low-temperature lithium-ion cell composite positive pole and preparation method thereof
CN107732220A (en) * 2017-11-27 2018-02-23 中南大学 The preparation method of the ternary cathode material of lithium ion battery of the mesoporous carbon coating of N doping

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
唐秀兰等: "不同质子酸掺杂对聚苯胺合成与性能的影响", 《塑料工业》 *
郭丽等: "锂蓄电池正极复合材料PEG_xPANI_yVXG的研究", 《电源技术》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109244430A (en) * 2018-11-13 2019-01-18 武汉科技大学 Polymer and nitrogen-doped carbon nanometer pipe are modified nickel cobalt manganese anode material and preparation method thereof altogether
CN110061234A (en) * 2019-05-27 2019-07-26 河南科技学院 A kind of anode material for lithium-ion batteries and preparation method thereof
CN110061234B (en) * 2019-05-27 2021-06-04 河南科技学院 Lithium ion battery anode material and preparation method thereof
CN112201791A (en) * 2020-10-23 2021-01-08 江苏大学 Method for improving ternary cathode material of lithium ion battery by oxygen-absorbing self-healing film
CN112563504A (en) * 2020-12-09 2021-03-26 北京理工大学重庆创新中心 Method for regulating and controlling surface transmission efficiency of lithium battery anode material and obtained anode material
CN114937766A (en) * 2022-05-31 2022-08-23 济宁学院 Preparation method of transition metal doped poly (m-phenylenediamine) -coated positive electrode material
CN114937766B (en) * 2022-05-31 2023-10-31 济宁学院 Preparation method of transition metal doped poly (m-phenylenediamine) coated positive electrode material
WO2024016467A1 (en) * 2022-07-20 2024-01-25 广东邦普循环科技有限公司 Preparation method for polymer/lithium nickel manganese oxide composite material, and product and use thereof
WO2024021273A1 (en) * 2022-07-27 2024-02-01 广东邦普循环科技有限公司 High-voltage ternary positive electrode material and preparation method therefor

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