CN105355849A - Lithium battery cathode additive, lithium ion battery, preparation method and uses thereof - Google Patents
Lithium battery cathode additive, lithium ion battery, preparation method and uses thereof Download PDFInfo
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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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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/366—Composites as layered products
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/139—Processes of manufacture
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Abstract
The invention discloses a lithium battery cathode additive, a lithium ion battery, a preparation method and uses thereof, and belongs to the technical field of lithium secondary battery. The cathode additive is a core-shell structure, wherein the core is composed of nanometer silicon powder, lithium powder compound and hollow carbon spheres, and the shell is composed of carbon nanotubes, surfactants and doping agents; the mass proportion of the nanometer silicon powder, the lithium powder compound and the hollow carbon spheres is 10-70:0.1-10:20-80; the mass proportion of the carbon nanotubes, surfactants, doping agents and nanometer silicon powder is 5-20:2.5-10:0.5-7:10-70; the lithium powder compound is a core-shell capsule constituted by lithium powder and polymer wrapping the lithium powder; the doping agents are sodium chloride and/or sodium fluoride; the surfactants is sodium dodecyl benzene sulfonate. The cathode additive is added to the graphite cathode, thereby obviously promotes gram volume, initial efficiency and circulation performance of the cathode materials and absorbing ability of the cathode plate.
Description
Technical field
The present invention relates to a kind of cathode of lithium battery additive, and the preparation method of cathode of lithium battery additive and application, the invention still further relates to a kind of lithium ion battery simultaneously, belong to technical field of lithium ion secondary.
Background technology
Negative material is the critical material of composition lithium ion battery, negative material used is mainly graphite material in the market, the problem that ubiquity gram volume low (372mAh/g), first efficiency is on the low side (88% ~ 95%), has a strong impact on the performance of cell integrated energy density.For improving the energy density of lithium ion battery, can improve from following two aspect anticathode materials: one is add silicon and compound thereof, improve the gram volume of negative material, two is the degree of graphitization improving negative material or the material added containing lithium, improves the efficiency first of negative material.
Silicon materials have higher specific capacity (up to 4200mAh/g), and it is rich reserves, with low cost, but there is huge change in volume in pure silicon material in battery charge and discharge process, this change can cause the efflorescence of pole piece, active material is come off from negative plate, cause being separated of electrode active material and collector, thus have a strong impact on the cycle performance of battery.Meanwhile, silicon materials are very easily reunited, and affect the cyclical stability of electrode.Therefore, directly silicon materials can not be used as negative material or additive.
Numerous known, the SEI that negative material surface is formed can consume a part of lithium ion, and efficiency is on the low side first to cause it, and the main path improving efficiency to be first anticathode material carry out graphitization processing, but increase rate is still very limited.The patent of invention of publication No. CN102148401A discloses one preferential formation SEI film before assembling lithium battery, and by providing lithium source, compensates the lithium that lithium battery loses in charge/discharge process first, thus the method that reduction irreversible capacity consumes.Simultaneously, the patent of invention of publication No. CN103779572A discloses a kind of cathode of lithium battery additive of tool nucleocapsid structure, be made up of simple substance lithium powder and the polymer (in zinc-containing solid catalyst/oxide, poly-alkylsiloxane, polyalkyl acrylate, polyalkyl methacrylate one or more) that is coated on lithium powder surface, wherein simple substance lithium powder stripping can participate in reaction, compensate the lithium that negative pole consumes when charge/discharge first, improve efficiency first, but little on the impact of gram volume raising.
At present, improve the energy density of negative material and be mostly solely to improve gram volume or efficiency first, the two is difficult to take into account simultaneously, and develops the energy density that high, that efficiency the is high first negative material of a kind of gram volume significantly could improve lithium battery.
Summary of the invention
The object of this invention is 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.
Moreover the present invention also provides a kind of application of cathode of lithium battery additive.
Finally, the present invention reoffers a kind of lithium battery adopting above-mentioned cathode additive agent.
In order to realize above object, the technical solution adopted in the present invention is:
Cathode of lithium battery additive, in nucleocapsid structure, kernel is made up of nano silica fume, lithium flour complexes, hollow carbon sphere, and shell is primarily of carbon nano-tube, surfactant, dopant composition; By quality ratio, nano silica fume: lithium flour complexes: hollow carbon sphere=10 ~ 70:0.1 ~ 10:20 ~ 80, carbon nano-tube: surfactant: dopant: nano silica fume=5 ~ 20:2.5 ~ 10:0.5 ~ 7:10 ~ 70.
Described lithium flour complexes is the nucleocapsid coating formed by lithium powder and the polymer that is coated on lithium powder surface, and polymer is one or more (see patent CN103779572A) in zinc-containing solid catalyst, polyalkylene oxides, poly-alkylsiloxane, polyalkyl acrylate and polyalkyl methacrylate.Specifically can select poly (propylene carbonate), poly-first and second base oxides, PES-4, polymethyl acrylate, polymethyl methacrylate.
Described dopant is sodium chloride and/or sodium fluoride.
Described surfactant is neopelex, and it act as and makes carbon nano-tube, dopant, nano silica fume dispersed in a solvent, improves the consistency of coating layer.
The preparation method of cathode of lithium battery additive, comprises the following steps:
1) accurately get each raw material according to mass ratio, nano silica fume, lithium flour complexes, hollow carbon sphere are mixed, obtains mixture A for subsequent use; Carbon nano-tube, surfactant are added in solvent, mixes, obtain mixture B for subsequent use;
2) mixture A is added in mixture B, after mixing at temperature 300 ~ 500 DEG C heat treatment 0.5 ~ 2h, mix after adding dopant, then at temperature 600 ~ 1000 DEG C carbonization treatment 1 ~ 10h.
Step 1) at dew point is not more than-50 DEG C, prepare mixture A.Step 2) at dew point is not more than-50 DEG C, mixture A is added in mixture B.The reason limiting dew point is that lithium flour complexes is very active in atmosphere, vigorous reaction can occur, there is certain potential safety hazard with water.Limit dew point simultaneously and can reduce the effect that lithium flour complexes provides lithium ion.
Step 1) in solvent be one or more in ethanol, acetone, carbon disulfide, carbon tetrachloride, oxolane, toluene, kerosene, liquid alkane, liquid cycloalkane, 1-METHYLPYRROLIDONE etc.The mass ratio of solvent and carbon nano-tube is 20:1 ~ 4.
Step 2) in the heating rate of carbonization treatment be 2 ~ 10 DEG C/min.
The application of cathode of lithium battery additive, is specially and adopts this additive to prepare graphite cathode.
Lithium battery, adopts the graphite cathode prepared by above-mentioned cathode additive agent.
Beneficial effect of the present invention:
The metal activity of simple substance lithium powder is strong, in atmosphere can not stable existence, if directly join in lithium cell cathode material, the making and use of giving battery is brought potential safety hazard.The present invention is by efficiently solving the problems referred to above in the polymer by coated for lithium powder, and polymer being soluble is in lithium battery electrolytes simultaneously, make coated after lithium powder stripping can participate in reaction, supplement the lithium that cathode of lithium battery consumes in charge/discharge process first.
Nano silica fume mixes with hollow carbon sphere by the present invention, the loose structure of hollow carbon sphere can be relied on the one hand, expansion in buffering pasc reaction process, combining nano silica flour height ratio capacity on the other hand, the advantage of hollow carbon sphere high expansion coefficient, high conductivity, reduce the adverse effect that composite material expands to whole pole piece, improve the gram volume of negative material simultaneously, and indirectly improve the energy density of material.Hollow carbon sphere has higher conductivity and specific area, has certain cushioning effect, can improve the cycle performance of material to the embedding structural deterioration going out to cause of lithium ion in cyclic process.And the sodium chloride that adulterates, sodium fluoride can improve the stability of clad structure, thus improve the cycle performance of material.This cathode additive agent is joined in graphite cathode, the imbibition ability of the gram volume of negative material, first efficiency, cycle performance and pole piece can be significantly improved.
In the present invention, the preparation technology of cathode of lithium battery additive is simple, easy and simple to handle, is suitable for suitability for industrialized production application.
Accompanying drawing explanation
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 embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Embodiment 1
Cathode of lithium battery additive in the present embodiment is nucleocapsid structure, and kernel is made up of nano silica fume, lithium flour complexes, hollow carbon sphere, and shell is primarily of carbon nano-tube, neopelex, NaF composition; Preparation process is as follows:
1) (kernel is 1g lithium powder by 50g nano silica fume, 5g lithium flour complexes first to adopt three-dimensional material mixer, outer core is poly-first and second base oxides of 4g, preparation method is with embodiment in patent CN103779572A 1), 60g hollow carbon sphere mixes under dew point-60 DEG C of conditions, obtains mixture A for subsequent use; 10g carbon nano-tube, 5g neopelex are added in 100g carbon tetrachloride solvent simultaneously, stir and make it mix, obtain mixture B for subsequent use;
2) under dew point-50 DEG C of conditions, mixture A is joined in mixture B, is uniformly mixed 1h, after mixing at temperature 300 DEG C heat treatment 0.5h solvent flashing, add 0.5gNaF again to mix, be warming up to 800 DEG C with the heating rate of 5 DEG C/min afterwards, carbonization treatment 5h and get final product.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 nucleocapsid structure, and kernel is made up of nano silica fume, lithium flour complexes, hollow carbon sphere, and shell is primarily of carbon nano-tube, neopelex, NaCl composition; Preparation process is as follows:
1) (kernel is 0.01g lithium powder by 10g nano silica fume, 0.1g lithium flour complexes first to adopt three-dimensional material mixer, outer core is 0.09g polymethyl methacrylate), 20g hollow carbon sphere mixes under dew point-50 DEG C of conditions, obtains mixture A for subsequent use; 20g carbon nano-tube, 10g neopelex are added in 100g toluene solvant simultaneously, stir and make it mix, obtain mixture B for subsequent use;
2) under dew point-60 DEG C of conditions, mixture A is joined in mixture B, is uniformly mixed 3h, after mixing at temperature 400 DEG C heat treatment 1h solvent flashing, add 5gNaCl again to mix, be warming up to 600 DEG C with the heating rate of 1 DEG C/min afterwards, carbonization treatment 10h and get final product.
Embodiment 3
Cathode of lithium battery additive in the present embodiment is nucleocapsid structure, and kernel is made up of nano silica fume, lithium flour complexes, hollow carbon sphere, and shell is primarily of carbon nano-tube, neopelex, NaCl composition; Preparation process is as follows:
1) first adopt three-dimensional material mixer 70g nano silica fume, 10g lithium flour complexes (kernel is 2g lithium powder, and outer core is 8g polymethyl acrylate), 80g hollow carbon sphere to be mixed under dew point-50 DEG C of conditions, obtain mixture A for subsequent use; 5g carbon nano-tube, 2.5g neopelex are added in 100g tetrahydrofuran solvent simultaneously, stir and make it mix, obtain mixture B for subsequent use;
2) under dew point-60 DEG C of conditions, mixture A is joined in mixture B, is uniformly mixed 5h, after mixing at temperature 500 DEG C heat treatment 2h solvent flashing, add 7gNaCl again to mix, be warming up to 1000 DEG C with the heating rate of 10 DEG C/min afterwards, carbonization treatment 1h and get final product.
Embodiment 4
Cathode of lithium battery additive in the present embodiment is nucleocapsid structure, and kernel is made up of nano silica fume, lithium flour complexes, hollow carbon sphere, and shell is primarily of carbon nano-tube, neopelex, NaF composition; Preparation process is as follows:
1) first adopt three-dimensional material mixer 25g nano silica fume, 3g lithium flour complexes (kernel is 2g lithium powder, and outer core is 8g polymethyl methacrylate), 40g hollow carbon sphere to be mixed under dew point-55 DEG C of conditions, obtain mixture A for subsequent use; 15g carbon nano-tube, 8g neopelex are added in 100g acetone solvent simultaneously, stir and make it mix, obtain mixture B for subsequent use;
2) under dew point-55 DEG C of conditions, mixture A is joined in mixture B, is uniformly mixed 3h, after mixing at temperature 450 DEG C heat treatment 1h solvent flashing, add 3gNaF again to mix, be warming up to 900 DEG C with the heating rate of 5 DEG C/min afterwards, carbonization treatment 3h and get final product.
Embodiment 5
Cathode of lithium battery additive in the present embodiment is nucleocapsid structure, and kernel is made up of nano silica fume, lithium flour complexes, hollow carbon sphere, and shell is primarily of carbon nano-tube, neopelex, NaCl composition; Preparation process is as follows:
1) first adopt three-dimensional material mixer 60g nano silica fume, 8g lithium flour complexes (kernel is 1g lithium powder, and outer core is 4g polymethyl acrylate), 70g hollow carbon sphere to be mixed under dew point-50 DEG C of conditions, obtain mixture A for subsequent use; 7.5g carbon nano-tube, 4g neopelex are added in 100g carbon disulfide solvent simultaneously, stir and make it mix, obtain mixture B for subsequent use;
2) under dew point-50 DEG C of conditions, mixture A is joined in mixture B, is uniformly mixed 2h, after mixing at temperature 350 DEG C heat treatment 2h solvent flashing, add 5gNaCl again to mix, be warming up to 800 DEG C with the heating rate of 8 DEG C/min afterwards, carbonization treatment 7h and get final product.
In other embodiments of the invention, step 2) in solvent also can adopt in ethanol, kerosene, 1-METHYLPYRROLIDONE, liquid alkane, liquid cycloalkane etc. any one.
Test example
1, electrical testing is detained
Respectively cathode of lithium battery additive prepared by embodiment 1 ~ 5 is joined in graphite, prepare negative plate successively and be assembled into button cell A1, A2, A3, A4, A5.Preparation method is: in graphite cathode material, add PVDF binding agent, cathode additive agent and nmp solvent, be coated in after stirring pulping on Copper Foil, dry, roll obtained negative plate, the amount ratio of graphite cathode material and additive, PVDF, NMP is 95g:1g:4g:220mL.Be to electrode with metal lithium sheet again, polypropylene (PP) is barrier film (or poly-second propylene, PEP), LiPF
6/ EC+DEC (EC, DEC volume ratio 1:1, concentration 1.3mol/L) is electrolyte, assembly simulation battery in the glove box filling hydrogen.
Adopt the chemical property of the blue electricity in Wuhan new prestige 5V/10mA type cell tester test battery A1, A2, A3, charging/discharging voltage is 0.005 ~ 2.0V, charge-discharge velocity 0.1C.Comparative example adopts conductive agent SP as cathode additive agent, and other are the same.Test the washing lotion ability of above-mentioned negative plate simultaneously.Button electrical test results sees the following form 1 and Fig. 2.
Table 1 electrochemical property test result
| Detain battery | 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 can be seen from Table 1, the button electricity battery adopting cathode additive agent in embodiment 1 ~ 5 to prepare, its first discharge capacity and efficiency all apparently higher than comparative example.Result shows, in the present invention, cathode additive agent can improve discharge capacity and the efficiency of battery.Reason is: containing the silicon of height ratio capacity in this cathode additive agent, can improve the gram volume of negative material, simultaneously containing the lithium ion material that can improve negative material efficiency first, can supplement the lithium ion consumed by battery SEI in time.Simultaneously owing to containing the large carbon nano-tube of specific area and air carbon ball in cathode additive agent, the imbibition liquid-keeping property of material on electrolyte obviously strengthens, the imbibition liquid-keeping property also corresponding enhancing of pole piece and battery core.
2, soft-package battery test
Join as negative material in Delanium using cathode additive agent prepared by embodiment 1 ~ 5 respectively, LiFePO4 is positive electrode, LiPF
6/ EC+DEC (EC, DEC volume ratio 1:1, concentration 1.3mol/L) is electrolyte, and Celgard2400 film is barrier film, preparation 5Ah soft-package battery A1, A2, A3.The cycle performance of above-mentioned battery is tested under multiplying power 1.0C/1.0C, voltage 2.7 ~ 4.2V condition.Comparative example adopts conductive agent SP as cathode additive agent, and other are the same.Electrochemical property test the results are shown in following table 2.
Table 2 electrochemical property test result
| Detain battery | 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 |
As can be seen from Table 2, adopt the soft-package battery that in embodiment 1 ~ 5 prepared by cathode additive agent, its cycle performance and first efficiency are all apparently higher than comparative example.Reason is: form SEI film when soft-package battery changes into constant volume first and need consume lithium ion, and lithium flour complexes can supplement the lithium ion consumed in time, improve the efficiency first of battery.Silicon simultaneously containing height ratio capacity in cathode additive agent, the gram volume of negative material can be improved and the energy density of indirect raising material, in addition hollow carbon sphere has higher conductivity and specific area, to the embedding structural deterioration going out to cause of lithium ion in cyclic process, there is certain cushioning effect, thus improve the cycle performance of material.
Claims (10)
1. cathode of lithium battery additive, is characterized in that: described cathode additive agent is nucleocapsid structure, and kernel is made up of nano silica fume, lithium flour complexes, hollow carbon sphere, and shell is primarily of carbon nano-tube, surfactant, dopant composition; By quality ratio, nano silica fume: lithium flour complexes: hollow carbon sphere=10 ~ 70:0.1 ~ 10:20 ~ 80, carbon nano-tube: surfactant: dopant: nano silica fume=5 ~ 20:2.5 ~ 10:0.5 ~ 7:10 ~ 70.
2. cathode additive agent according to claim 1, it is characterized in that: described lithium flour complexes is the nucleocapsid coating formed by lithium powder and the polymer that is coated on lithium powder surface, polymer is one or more in zinc-containing solid catalyst, polyalkylene oxides, poly-alkylsiloxane, polyalkyl acrylate and polyalkyl methacrylate.
3. cathode additive agent according to claim 1, is characterized in that: described dopant is sodium chloride and/or sodium fluoride.
4. cathode additive agent according to claim 1, is characterized in that: described surfactant is neopelex.
5. the preparation method of cathode additive agent according to any one of Claims 1 to 4, is characterized in that: comprise the following steps:
1) accurately get each raw material according to mass ratio, nano silica fume, lithium flour complexes, hollow carbon sphere are mixed, obtains mixture A for subsequent use; Carbon nano-tube, surfactant are added in solvent, mixes, obtain mixture B for subsequent use;
2) mixture A is added in mixture B, after mixing at temperature 300 ~ 500 DEG C heat treatment 0.5 ~ 2h, mix after adding dopant, then at temperature 600 ~ 1000 DEG C carbonization treatment 1 ~ 10h.
6. preparation method according to claim 5, is characterized in that: step 1) in solvent be one or more in ethanol, acetone, carbon disulfide, carbon tetrachloride, oxolane, toluene, kerosene, liquid alkane, liquid cycloalkane, 1-METHYLPYRROLIDONE.
7. preparation method according to claim 5, is characterized in that: the mass ratio of solvent and carbon nano-tube is 20:1 ~ 4.
8. preparation method according to claim 5, is characterized in that: step 2) in the heating rate of carbonization treatment be 2 ~ 10 DEG C/min.
9. the application of cathode additive agent according to any one of Claims 1 to 4, is characterized in that: adopt this cathode additive agent to prepare graphite cathode.
10. lithium battery, is characterized in that: adopt the graphite cathode that according to any one of Claims 1 to 4 prepared by cathode additive agent.
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Cited By (8)
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| 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 |
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| CN110521029A (en) * | 2017-02-09 | 2019-11-29 | 株式会社村田制作所 | Secondary cell, battery pack, electric vehicle, electric tool and electronic equipment |
| CN112467123A (en) * | 2020-08-14 | 2021-03-09 | 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 |
| CN112670479A (en) * | 2020-12-24 | 2021-04-16 | 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 |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
-
2015
- 2015-11-18 CN CN201510798929.8A patent/CN105355849B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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