CN105355849B - Cathode of lithium battery additive, lithium ion battery, preparation method and application - Google Patents
Cathode of lithium battery additive, lithium ion battery, preparation method and application Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a kind of cathode of lithium battery additive, lithium ion battery, preparation method and application, belong to technical field of lithium ion secondary.The cathode additive agent is in core shell structure, and kernel is made up of nano silica fume, lithium flour complexes, hollow carbon sphere, and shell is mainly made up of CNT, surfactant, dopant；By quality ratio, nano silica fume:Lithium flour complexes:Hollow carbon sphere=10~70:0.1~10:20~80, CNT:Surfactant:Dopant:Nano silica fume=5~20:2.5~10:0.5~7:10~70；Lithium flour complexes are by lithium powder and are coated on the nucleocapsid coating that the polymer on lithium powder surface is formed, and dopant is sodium chloride and/or sodium fluoride, and surfactant is neopelex.The cathode additive agent is added in graphite cathode, gram volume, the imbibition ability of efficiency, cycle performance and pole piece first of negative material can be significantly improved.
Description
Technical field
The present invention relates to the preparation method and application of a kind of cathode of lithium battery additive, and cathode of lithium battery additive,
Simultaneously the invention further relates to a kind of lithium ion battery, belong to technical field of lithium ion secondary.
Background technology
Negative material is the critical material for constituting lithium ion battery, and negative material used is mainly graphite material in the market
Material, generally existing gram volume low (372mAh/g), first efficiency relatively low (88%~95%) the problem of, have a strong impact on battery overall
The performance of energy density.To improve the energy density of lithium ion battery, negative material can be changed in terms of following two
Enter：One is addition silicon and its compound, improves the gram volume of negative material, and two be degree of graphitization or the addition for improving negative material
Material containing lithium, improves the efficiency first of negative material.
Silicon materials have a higher specific capacity (up to 4200mAh/g), and rich reserves, with low cost, but pure silicon material
Material there are huge Volume Changes in battery charge and discharge process, this change can cause the efflorescence of pole piece, make active material from
Come off on negative plate, cause the separation of electrode active material and collector, so as to have a strong impact on the cycle performance of battery.Meanwhile,
Silicon materials are easily reunited, and influence the cyclical stability of electrode.It is thus impossible to which silicon materials directly are used as into negative material or addition
Agent.
It is numerous known, negative material surface formed SEI can consume a part of lithium ion, cause its first efficiency it is relatively low,
And the main path for improving efficiency first is that graphitization processing is carried out to negative material, but increase rate is still very limited.It is public
Cloth CN102148401A patent of invention discloses one kind and preferentially forms SEI films before assembling lithium battery, and by providing lithium
Source, the lithium that compensation lithium battery loses during charge/discharge first, so as to reduce the method for irreversible capacity consumption.Meanwhile, it is public
Cloth CN103779572A patent of invention discloses a kind of cathode of lithium battery additive for having core shell structure, by elemental lithium powder and
It is coated on polymer (zinc-containing solid catalyst/oxide, polyalkylsiloxane, polyalkyl acrylate, the poly- first on lithium powder surface
One or more in base alkyl acrylate) composition, wherein elemental lithium powder can dissolution participate in reaction, compensation negative pole first
The lithium consumed during charge/discharge, improves efficiency first, but the influence improved to gram volume is little.
At present, the energy density for improving negative material is solely to improve gram volume or first efficiency mostly, and the two is difficult to
Take into account simultaneously, and develop a kind of gram volume it is high, first the negative material of efficiency high can just greatly improve the energy density of lithium battery.
The content of the invention
It is an object of the invention to provide a kind of cathode of lithium battery additive.
Meanwhile, the present invention also provides a kind of preparation method of cathode of lithium battery additive.
Furthermore, the present invention also provides a kind of application of cathode of lithium battery additive.
Finally, the present invention provides a kind of lithium battery using above-mentioned cathode additive agent again.
In order to realize the above object the technical solution adopted in the present invention is：
Cathode of lithium battery additive, in core shell structure, kernel is made up of nano silica fume, lithium flour complexes, hollow carbon sphere, outside
Shell is mainly made up of CNT, surfactant, dopant；By quality ratio, nano silica fume:Lithium flour complexes:Hollow carbon
Ball=10~70:0.1~10:20~80, CNT:Surfactant:Dopant:Nano silica fume=5~20:2.5~10:
0.5~7:10~70.
The lithium flour complexes are by lithium powder and to be coated on the nucleocapsid coating that the polymer on lithium powder surface is formed, polymer
For zinc-containing solid catalyst, polyalkylene oxides, polyalkylsiloxane, polyalkyl acrylate and alkyl methacrylate polymer
One or more in ester (referring to patent CN103779572A).Poly (propylene carbonate), poly- first and second base oxide are specifically can select,
PES-4, PMA, polymethyl methacrylate.
The dopant is sodium chloride and/or sodium fluoride.
The surfactant is neopelex, and it act as making CNT, dopant, nano silica fume exist
It is dispersed in solvent, improve the uniformity of clad.
The preparation method of cathode of lithium battery additive, comprises the following steps：
1) each raw material is accurately taken according to mass ratio, nano silica fume, lithium flour complexes, hollow carbon sphere are well mixed, obtain mixed
Compound A is standby；CNT, surfactant are added in solvent, is well mixed, obtains mixture B standby；
2) mixture A is added in mixture B, 0.5~2h is heat-treated at 300~500 DEG C of temperature after being well mixed, plus
Enter and mixed after dopant, then 1~10h of carbonization treatment at 600~1000 DEG C of temperature.
Step 1) in prepare mixture A in the case where dew point is not more than -50 DEG C.Step 2) in the case where dew point is not more than -50 DEG C will
Mixture A is added in mixture B.The reason for limiting dew point is that lithium flour complexes are very active in atmosphere, can occur play with water
, there is certain potential safety hazard in strong reaction.The effect that lithium flour complexes provide lithium ion can be reduced by limiting dew point simultaneously.
Step 1) in solvent be ethanol, acetone, carbon disulfide, carbon tetrachloride, tetrahydrofuran, toluene, kerosene, liquid alkane
One or more in hydrocarbon, liquid cycloalkane, 1-METHYLPYRROLIDONE etc..The mass ratio of solvent and CNT is 20:1~4.
Step 2) in carbonization treatment heating rate be 2~10 DEG C/min.
The application of cathode of lithium battery additive, specially prepares graphite cathode using the additive.
Lithium battery, using the graphite cathode prepared by above-mentioned cathode additive agent.
Beneficial effects of the present invention：
The metal activity of elemental lithium powder is strong, can not be stabilized in atmosphere, if being added directly into lithium ion battery anode material
In material, by the making of battery and using bringing potential safety hazard.The present invention is by the way that lithium powder cladding is effectively solved in the polymer
Above mentioned problem, while polymer dissolves in lithium battery electrolytes so that lithium powder after cladding can dissolution participate in reaction, supplement
The lithium that cathode of lithium battery is consumed during charge/discharge first.
The present invention mixes nano silica fume with hollow carbon sphere, on the one hand can rely on the loose structure of hollow carbon sphere, buffer silicon
Expansion in course of reaction, on the other hand with reference to nano silica fume height ratio capacity, hollow carbon sphere high expansion coefficient, high conductivity it is excellent
Point, reduction composite expansion while improving the gram volume of negative material, and improves material indirectly to the adverse effect of whole pole piece
The energy density of material.Hollow carbon sphere has higher electric conductivity and specific surface area, embedding to lithium ion in cyclic process to go out to cause
Structure destruction has certain cushioning effect, can improve the cycle performance of material.And the sodium chloride that adulterates, sodium fluoride can improve cladding
The stability of structure, so as to improve the cycle performance of material.The cathode additive agent is added in graphite cathode, can be significantly improved
The imbibition ability of the gram volume of negative material, first efficiency, cycle performance and pole piece.
The preparation technology of cathode of lithium battery additive is simple in the present invention, easy to operate, suitable for industrialized production and application.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of cathode of lithium battery additive in embodiment 1；
Fig. 2 is the electrochemical property test curve of button cell in test example 1.
Embodiment
Following embodiments are only described in further detail to the present invention, but do not constitute any limitation of the invention.
Embodiment 1
Cathode of lithium battery additive in the present embodiment is core shell structure, and kernel is by nano silica fume, lithium flour complexes, hollow
Carbon ball is constituted, and shell is mainly made up of CNT, neopelex, NaF；Preparation process is as follows：
1) using three-dimensional material mixer first, (kernel is 4g for 1g lithium powder, outer core by 50g nano silica fumes, 5g lithiums flour complexes
Poly- first and second base oxide, preparation method is with embodiment 1 in patent CN103779572A), 60g hollow carbon spheres are in -60 DEG C of bars of dew point
It is well mixed under part, obtains mixture A standby；10g CNTs, 5g neopelexes are added to 100g tetrachloros simultaneously
Change in carbon solvent, stirring is well mixed it, obtains mixture B standby；
2) under the conditions of -50 DEG C of dew point, mixture A is added in mixture B, stirring mixing 1h, in temperature after mixing
0.5h solvent flashings are heat-treated at 300 DEG C, 0.5g NaF is added and is well mixed, heated up afterwards with 5 DEG C/min heating rate
To 800 DEG C, carbonization treatment 5h is produced.The scanning electron microscope (SEM) photograph of gained cathode additive agent is shown in Fig. 1.
Embodiment 2
Cathode of lithium battery additive in the present embodiment is core shell structure, and kernel is by nano silica fume, lithium flour complexes, hollow
Carbon ball is constituted, and shell is mainly made up of CNT, neopelex, NaCl；Preparation process is as follows：
1) using three-dimensional material mixer first, (kernel is 0.01g lithium powder, outer core by 10g nano silica fumes, 0.1g lithiums flour complexes
For 0.09g polymethyl methacrylates), 20g hollow carbon spheres be well mixed under the conditions of -50 DEG C of dew point, obtain mixture A standby；
20g CNTs, 10g neopelexes are added in 100g toluene solvants simultaneously, stirring is well mixed it, obtains
Mixture B is standby；
2) under the conditions of -60 DEG C of dew point, mixture A is added in mixture B, stirring mixing 3h, in temperature after mixing
1h solvent flashings are heat-treated at 400 DEG C, 5g NaCl is added and is well mixed, be warming up to afterwards with 1 DEG C/min heating rate
600 DEG C, carbonization treatment 10h is produced.
Embodiment 3
Cathode of lithium battery additive in the present embodiment is core shell structure, and kernel is by nano silica fume, lithium flour complexes, hollow
Carbon ball is constituted, and shell is mainly made up of CNT, neopelex, NaCl；Preparation process is as follows：
1) using three-dimensional material mixer first, (kernel is 8g for 2g lithium powder, outer core by 70g nano silica fumes, 10g lithiums flour complexes
PMA), 80g hollow carbon spheres be well mixed under the conditions of -50 DEG C of dew point, obtain mixture A standby；5g carbon is received simultaneously
Mitron, 2.5g neopelexes are added in 100g tetrahydrofuran solvents, and stirring is well mixed it, obtains mixture B
It is standby；
2) under the conditions of -60 DEG C of dew point, mixture A is added in mixture B, stirring mixing 5h, in temperature after mixing
2h solvent flashings are heat-treated at 500 DEG C, 7g NaCl is added and is well mixed, be warming up to afterwards with 10 DEG C/min heating rate
1000 DEG C, carbonization treatment 1h is produced.
Embodiment 4
Cathode of lithium battery additive in the present embodiment is core shell structure, and kernel is by nano silica fume, lithium flour complexes, hollow
Carbon ball is constituted, and shell is mainly made up of CNT, neopelex, NaF；Preparation process is as follows：
1) using three-dimensional material mixer first, (kernel is 8g for 2g lithium powder, outer core by 25g nano silica fumes, 3g lithiums flour complexes
Polymethyl methacrylate), 40g hollow carbon spheres be well mixed under the conditions of -55 DEG C of dew point, obtain mixture A standby；Simultaneously will
15g CNTs, 8g neopelexes are added in 100g acetone solvents, and stirring is well mixed it, obtains mixture B
It is standby；
2) under the conditions of -55 DEG C of dew point, mixture A is added in mixture B, stirring mixing 3h, in temperature after mixing
1h solvent flashings are heat-treated at 450 DEG C, 3g NaF is added and is well mixed, be warming up to 900 afterwards with 5 DEG C/min heating rate
DEG C, carbonization treatment 3h is produced.
Embodiment 5
Cathode of lithium battery additive in the present embodiment is core shell structure, and kernel is by nano silica fume, lithium flour complexes, hollow
Carbon ball is constituted, and shell is mainly made up of CNT, neopelex, NaCl；Preparation process is as follows：
1) using three-dimensional material mixer first, (kernel is 4g for 1g lithium powder, outer core by 60g nano silica fumes, 8g lithiums flour complexes
PMA), 70g hollow carbon spheres be well mixed under the conditions of -50 DEG C of dew point, obtain mixture A standby；Simultaneously by 7.5g carbon
Nanotube, 4g neopelexes are added in 100g carbon disulfide solvents, and stirring is well mixed it, obtains mixture B
It is standby；
2) under the conditions of -50 DEG C of dew point, mixture A is added in mixture B, stirring mixing 2h, in temperature after mixing
2h solvent flashings are heat-treated at 350 DEG C, 5g NaCl is added and is well mixed, be warming up to afterwards with 8 DEG C/min heating rate
800 DEG C, carbonization treatment 7h is produced.
In other embodiments of the invention, step 2) in solvent can also using ethanol, kerosene, 1-METHYLPYRROLIDONE,
Any of liquid alkane, liquid cycloalkane etc..
Test example
1st, electrical testing is detained
The cathode of lithium battery additive respectively prepared by embodiment 1~5 is added in graphite, is sequentially prepared negative plate and group
Dress up button cell A1, A2, A3, A4, A5.Preparation method is：PVDF binding agents, negative pole addition are added in graphite cathode material
It is coated in after agent and nmp solvent, stirring pulping on copper foil, dries, rolls obtained negative plate, graphite cathode material and additive,
PVDF, NMP amount ratio are 95g:1g:4g:220mL.Again using metal lithium sheet as to electrode, polypropylene (PP) is that barrier film is (or poly-
Second propylene, PEP), LiPF6/ EC+DEC (EC, DEC volume ratios 1:1, concentration 1.3mol/L) it is electrolyte, it is being flushed with hydrogen the gloves of gas
Assembly simulation battery in case.
Using new prestige 5V/10mA types cell tester test battery A1, A2, the A3 of the blue electricity in Wuhan chemical property, charge and discharge
Piezoelectric voltage is 0.005~2.0V, charge-discharge velocity 0.1C.Comparative example is using conductive agent SP as cathode additive agent, and other are ibid.
The washing lotion ability of above-mentioned negative plate is tested simultaneously.Button electrical test results see the table below 1 and Fig. 2.
The electrochemical property test result of table 1
| The electric battery of button | A1 | A2 | A3 | A4 | A5 | Comparative example |
| Cathode additive agent | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | SP |
| Discharge capacity (mAh/g) first | 394.1 | 395.4 | 391.8 | 389.7 | 391.2 | 339.5 |
| Efficiency (%) first | 99.1 | 98.8 | 98.3 | 98.2 | 98.3 | 92.4 |
| Rate of liquid aspiration (ml/min) | 4.9 | 4.8 | 4.7 | 4.6 | 4.7 | 3.3 |
As it can be seen from table 1 the electric battery of the button prepared using cathode additive agent in embodiment 1~5, its discharge capacity first
With efficiency obviously higher than comparative example.As a result show, cathode additive agent can improve the discharge capacity and efficiency of battery in the present invention.
Reason is：Silicon containing height ratio capacity in the cathode additive agent, can improve the gram volume of negative material, simultaneously containing can improve
The lithium ion material of negative material efficiency first, the lithium ion consumed by battery SEI can be supplemented in time.Simultaneously because negative pole is added
Containing the big CNT of specific surface area and air carbon ball in agent, the imbibition liquid-keeping property of material on electrolyte is remarkably reinforced, pole
Piece and the imbibition liquid-keeping property of battery core also accordingly strengthen.
2nd, soft-package battery is tested
The cathode additive agent respectively prepared by embodiment 1~5, which is added in Delanium, is used as negative material, LiFePO4
For positive electrode, LiPF6/ EC+DEC (EC, DEC volume ratios 1:1, concentration 1.3mol/L) it is electrolyte, the films of Celgard 2400
For barrier film, 5Ah soft-package batteries A1, A2, A3 are prepared.Above-mentioned electricity is tested under the conditions of multiplying power 1.0C/1.0C, 2.7~4.2V of voltage
The cycle performance in pond.Comparative example is using conductive agent SP as cathode additive agent, and other are ibid.Electrochemical property test result is seen below
Table 2.
The electrochemical property test result of table 2
| The electric battery of button | A1 | A2 | A3 | A4 | A5 | Comparative example |
| Cathode additive agent | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | SP |
| Initial charge capacity/Ah | 5.81 | 5.87 | 5.79 | 5.81 | 5.80 | 5.93 |
| Discharge capacity/Ah first | 5.47 | 5.51 | 5.42 | 5.44 | 5.43 | 5.21 |
| Efficiency/% first | 94.20 | 93.90 | 93.70 | 93.65 | 93.67 | 87.80 |
| Battery weight/g | 126.04 | 127.08 | 126.59 | 126.23 | 127.01 | 131.45 |
| Energy density/Wh/kg | 138.95 | 138.80 | 137.14 | 137.25 | 136.81 | 126.83 |
| 60 DEG C, 500 circulation conservation rates (%) | 95.5 | 94.9 | 94.7 | 94.6 | 94.5 | 91.7 |
From table 2 it can be seen that the soft-package battery prepared using cathode additive agent in embodiment 1~5, its cycle performance and head
Secondary efficiency is obviously higher than comparative example.Reason is：SEI films are formed when soft-package battery is melted into constant volume first need to consume lithium ion,
And lithium flour complexes can supplement the lithium ion of consumption in time, the efficiency first of battery is improved.Contain height in cathode additive agent simultaneously
The silicon of specific capacity, can improve negative material gram volume and indirectly improve material energy density, in addition hollow carbon sphere have compared with
High electric conductivity and specific surface area, it is embedding to lithium ion in cyclic process go out cause structure destruction have certain cushioning effect,
So as to improve the cycle performance of material.
Claims (10)
1. cathode of lithium battery additive, it is characterised in that：The cathode additive agent is in core shell structure, and kernel is by nano silica fume, lithium
Flour complexes, hollow carbon sphere composition, shell are made up of CNT, surfactant, dopant；By quality ratio, nano-silicon
Powder:Lithium flour complexes:Hollow carbon sphere=10~70:0.1~10:20~80, CNT:Surfactant:Dopant:Nanometer
Silica flour=5~20:2.5~10:0.5~7:10~70.
2. cathode additive agent according to claim 1, it is characterised in that：The lithium flour complexes are by lithium powder and are coated on
The nucleocapsid coating of the polymer formation on lithium powder surface, polymer is zinc-containing solid catalyst, polyalkylene oxides, poly- alkyl
One or more in siloxanes, polyalkyl acrylate and polyalkyl methacrylate.
3. cathode additive agent according to claim 1, it is characterised in that：The dopant is sodium chloride and/or sodium fluoride.
4. cathode additive agent according to claim 1, it is characterised in that：The surfactant is DBSA
Sodium.
5. the preparation method of cathode additive agent as any one of Claims 1 to 4, it is characterised in that：Comprise the following steps：
1) each raw material is accurately taken according to mass ratio, nano silica fume, lithium flour complexes, hollow carbon sphere are well mixed, mixture A is obtained
It is standby；CNT, surfactant are added in solvent, is well mixed, obtains mixture B standby；
2) mixture A is added in mixture B, is heat-treated 0.5~2h at 300~500 DEG C of temperature after being well mixed, addition is mixed
Mixed after miscellaneous dose, then 1~10h of carbonization treatment at 600~1000 DEG C of temperature.
6. preparation method according to claim 5, it is characterised in that：Step 1) in solvent be ethanol, acetone, curing
One or more in carbon, carbon tetrachloride, tetrahydrofuran, toluene, kerosene, liquid alkane, 1-METHYLPYRROLIDONE.
7. preparation method according to claim 5, it is characterised in that：The mass ratio of solvent and CNT is 20:1~4.
8. preparation method according to claim 5, it is characterised in that：Step 2) in carbonization treatment heating rate for 2~
10℃/min。
9. the application of cathode additive agent as any one of Claims 1 to 4, it is characterised in that：Using the cathode additive agent
Prepare graphite cathode.
10. lithium battery, it is characterised in that：The graphite prepared using the cathode additive agent as any one of Claims 1 to 4 is born
Pole.
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| CN106450170A (en) * | 2016-10-25 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Production method of low-cost and high-quality lithium-ion battery |
| WO2018146865A1 (en) * | 2017-02-09 | 2018-08-16 | 株式会社村田製作所 | Secondary battery, battery pack, electric vehicle, electric tool and electronic device |
| CN106711428A (en) * | 2017-03-22 | 2017-05-24 | 江苏元景锂粉工业有限公司 | Lithium-rich ternary composite material and preparation method thereof |
| CN107068999A (en) * | 2017-03-22 | 2017-08-18 | 江苏元景锂粉工业有限公司 | A kind of trielement composite material of core shell structure and preparation method thereof |
| CN107768644B (en) * | 2017-10-20 | 2020-04-07 | 乌兰察布市大盛石墨新材料股份有限公司 | Sulfur-doped graphite composite material and preparation method thereof |
| CN112909224A (en) * | 2019-12-04 | 2021-06-04 | 华为技术有限公司 | Lithium ion battery electrode material and preparation method thereof |
| CN112467123B (en) * | 2020-08-14 | 2022-06-10 | 珠海中科兆盈丰新材料科技有限公司 | High-capacity lithium ion battery cathode material and preparation method thereof |
| CN112670479B (en) * | 2020-12-24 | 2022-08-09 | 惠州亿纬锂能股份有限公司 | Sulfur and nitrogen co-doped coaxial core-shell silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
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| CN103779572A (en) * | 2012-10-26 | 2014-05-07 | 华为技术有限公司 | Lithium ion battery cathode additive and preparation method thereof, lithium ion battery cathode piece and lithium ion battery |
| CN104332608A (en) * | 2014-08-19 | 2015-02-04 | 新乡远东电子科技有限公司 | Lithium ion battery silicon composite negative electrode material and preparation method thereof |
| KR20150067627A (en) * | 2013-12-10 | 2015-06-18 | 충북대학교 산학협력단 | Method for synthesis of Silicon/Carbon composite as the lithium secondary battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1937285A (en) * | 2005-09-23 | 2007-03-28 | 中国科学院物理研究所 | Method for preparing lithium secondary cell electrode containing nano additive |
| CN102403506A (en) * | 2010-09-10 | 2012-04-04 | 威力能源股份有限公司 | Lithium ion battery negative electrode material additive, lithium ion battery and negative electrode material thereof |
| CN103779572A (en) * | 2012-10-26 | 2014-05-07 | 华为技术有限公司 | Lithium ion battery cathode additive and preparation method thereof, lithium ion battery cathode piece and lithium ion battery |
| KR20150067627A (en) * | 2013-12-10 | 2015-06-18 | 충북대학교 산학협력단 | Method for synthesis of Silicon/Carbon composite as the lithium secondary battery anode material |
| CN104332608A (en) * | 2014-08-19 | 2015-02-04 | 新乡远东电子科技有限公司 | Lithium ion battery silicon composite negative electrode material and preparation method thereof |
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