CN104528728A - Method for synthesizing nano-silicon powder by using silicon tetrachloride as raw material and application of nano-silicon powder - Google Patents
Method for synthesizing nano-silicon powder by using silicon tetrachloride as raw material and application of nano-silicon powder Download PDFInfo
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Abstract
The invention relates to a method for synthesizing nano-silicon powder by using silicon tetrachloride as a raw material and an application of the nano-silicon powder. The invention belongs to the field of nano-silicon powder preparation and application and specifically relates to a technology for preparing high-performance nano-silicon powder in a molten salt system at low temperature by using silicon tetrachloride as a raw material. The prepared nano-silicon powder is used as a lithium ion battery cathode material.
Description
Technical field
The present invention relates to the preparations and applicatio field of nano silica fume, relate to a kind of is particularly the technique of raw material low-temperature growth high performance silicon nano powder with silicon tetrachloride in molten salt system, and prepared silicon nano power is used as lithium ion battery negative material.
Background technology
Based on application important on function electronics, the preparation of silicon nano material causes to be paid close attention to widely.Meanwhile, silicon nano material can applied, owing to having high theoretical capacity (~ 4200mAh g by charging-discharging lithium ion battery
-1) and low discharge potential (<0.5V, Li/Li
+) be considered to replace traditional negative pole best material.
Traditionally, silicon materials mainly adopt solid phase reduction silicon-dioxide to prepare.Such as higher than the carbothermic reduction silicon-dioxide (document 1, Nagamori, M., Malinsky, I. & Claveau, A.Metall.Trans.B17,503 – 514 (1986)) of 2000 DEG C; Magnesiothermic reduction (document 2, Bao Z, Weatherspoon M R when 650 DEG C, Shian S, et al., Nature, 446:172-175,) and the electrochemical reduction (document 3 be greater than under 850 DEG C of conditions (2007), Cho S K, Fan F R F, Bard A J., Angewandte Chemie, 124:12912-12916 (2012)).In the recent period, in order to synthesize the nano silicon material that can be applied to lithium cell cathode material, a large amount of synthetic methods is developed.Such as, by chemical Vapor deposition process, 400 DEG C of pyrolysis SiH in the reactor that pressure is 3Torr
4/ H
2and PH (50%)
3/ H
2(100ppm) gas mixture, and porous alumina be template auxiliary under prepare silicon nanowires, this nano wire illustrates long cycle life (after 1100 circle charge and discharges circulations, capacity is 1029mAh/g) and high high rate performance, and (under 10 multiplying powers, capacity is ~ 956mAh g
-1) (document 4, Cho J H, Picraux S T.Nano letters, 13:5740-5747 (2013)).Silicon nano material better performances prepared by this technology, but method is expensive.Silicon tetrachloride is the important source material of synthesis silicon nano material, the mainly preparation in organic solvent of synthesis in the past, the people such as Heath reported first in 1992 in organic phase sodium reduction silicon tetrachloride prepare the method for silicon nanocluster, the method needs 385 DEG C of reactions, 3 to 7 days (documents 5 in steel bomb, Heath J R., Science, 258:1131-1133 (1992)).Subsequently, the people such as Jaephil Cho use similar preparation method to synthesize nano silicon particles, present high charging capacity (3535mAh g-1) after this particle is coated by further carbon and after 40 circles that circulate capacity keep 96% (document 6, Kim H, Seo M, Park M H, et al.Angew.Chem.Inter.Ed., 49:2146-2149 (2010)).Therefore, the eco-friendly low-temperature synthetic method of development silicon nano power, to the preparation of the scale of silicon nano material and silicon significant as the practical application of high-performance lithium ion negative material.
Summary of the invention
The object of the present invention is to provide a kind of low temperature preparation method of silicon nano power.Under low-temperature molten salt system, use cheap silicon source, temperature of reaction reduces further, not with an organic solvent, solves current silicon nano material preparation feedback condition harsh, the problem of expensive starting materials.This silicon nano power body, as lithium cell negative pole energy material, has excellent chemical property, effectively solves the actual application problem of silicon as high-performance lithium ion negative material.Compared with bibliographical information, required raw material is cheap, and temperature of reaction is lower, preparation flow environmental protection, and productive rate is higher, and production cost is low, is beneficial to amplify to produce.
Specifically, the invention provides the following:
1. prepare a method for silicon nano power, under described method is included in the fused salt condition of 200 DEG C ~ 500 DEG C, with metallic reducing silicon tetrachloride to synthesize the step of silicon nano power.
2. the method according to 1, described metal is selected from sodium Metal 99.5, magnesium powder, the one in aluminium powder or several, or its corresponding metal alloy.
3. the method according to 1, described fused salt is selected from Aluminum chloride anhydrous, Zinc Chloride Anhydrous, Magnesium Chloride Anhydrous, one or several in anhydrous chlorides of rase sodium.
4. the method according to 1, the reaction times of described reduction is 5 hours to 3 days, is preferably 5-20 hour.
5. the method according to 1, the temperature of reaction of described reduction is 200 DEG C ~ 400 DEG C.
6. the method according to 1, described method also comprises washing, pickling, hydrofluoric acid dips removing impurity and the step of filtration drying after reduction reaction.
7. the method according to 1, described reduction is carried out in stainless steel cauldron.
8. the method according to 1, described silicon nano power is unbodied nano-scale particle.
9. a silicon nano power, described silicon nano power is prepared by the method described in any one of 1-8.
Silicon nano power described in 10 is used for the purposes of lithium cell cathode material.
Detailed Description Of The Invention
First aspect of the present invention provides a kind of molten salt react ion to prepare the method for silicon nano power, under low-temperature molten salt condition, with the cheap silicon source of metallic reducing, and synthesis silicon nano power.The reduction reaction that described method adopts fused salt to participate in, realizes preparation in macroscopic quantity silicon materials.
In preferred embodiments, described silicon source is the silicon tetrachloride of technical grade.
In preferred embodiments, described metal is selected from sodium Metal 99.5, magnesium powder, the one in aluminium powder or several, or its corresponding metal alloy.
In preferred embodiments, described fused salt is selected from Aluminum chloride anhydrous, Zinc Chloride Anhydrous, Magnesium Chloride Anhydrous, one or several in anhydrous chlorides of rase sodium.
In preferred embodiments, the temperature of reaction of described reduction is 200 DEG C ~ 500 DEG C; Reaction times be 5h by 3 days, be preferably 5 ~ 20h.
In preferred embodiments, the temperature of reaction of described reduction is 200 DEG C ~ 400 DEG C
In preferred embodiments, described reduction can be carried out in stainless steel cauldron.
In preferred embodiments, described silicon nano power is unbodied nano-scale particle.
In preferred embodiments, described method also comprises washing, pickling, hydrofluoric acid dips removing impurity and the step of filtration drying.
In a more preferred embodiment, metal and silicon tetrachloride is adopted to press chemical reaction equivalent proportioning, and mix with excessive aluminum chloride, be sealed in the autoclave of 20mL ~ 3L, in 200 DEG C ~ 500 DEG C reaction 300 minutes to 3 days, head product through washing, pickling, after hydrofluoric acid dips removing impurity, namely filtration drying obtains the silicon nano power body of pure phase;
Second aspect of the present invention provides a kind of silicon nano power, and described silicon nanometer divides method preparation described according to a first aspect of the present invention.
In a preferred embodiment, prepared silicon nano power can reach 70% even higher productive rate.
3rd aspect of the present invention provides the silicon nano power described in the present invention second aspect for the purposes of lithium ion battery negative material, when this powder is used for lithium ion battery negative material, show higher lithium storage content, high coulombic efficiency and long cyclical stability.
Advantage of the present invention and positively effect:
With existing carbon heat, the technology such as magnesiothermic reduction silicon oxide are compared, and the temperature needed for the method for the invention is low, and productive rate is higher.Compared with the technology such as existing organic liquid phase reduction, the cheap and good process of raw material of the present invention;
Silicon source of the present invention is the silicon tetrachloride of technical grade, is also a kind of byproduct of polysilicon industry.
The simple environmental protection of preparation flow of the present invention, is beneficial to amplify and produces.
The silica flour that the present invention obtains is the particle of nano-scale, has good pattern, uniform particles micro-nano structure, and grain crystalline can according to the adjustment of reflection temperature.
Silicon nanoparticle prepared by the present invention, during for lithium ion battery negative, demonstrates the lithium storage content far above graphite cathode.
The silicon nano power of the present invention's synthesis, be assembled into lithium ion battery, its lithium storage content higher than 1400mAh/g, can improve 4 times compared with the 372mAh/g of graphite negative electrodes, and has long circulation life.
Accompanying drawing explanation
Fig. 1 is the x-ray diffractogram of the silicon nano power body that embodiment 1 obtains;
Fig. 2 is the transmission electron microscope picture of the silicon nano power body that embodiment 1 obtains;
Fig. 3 is the scanning electron microscope (SEM) photograph of the silicon nano power body that embodiment 1 obtains;
Fig. 4 is the x-ray diffractogram of the silicon nano power body that embodiment 2 obtains;
Fig. 5 is the x-ray diffractogram of the silicon nano power body that embodiment 3 obtains;
Fig. 6 is the x-ray diffractogram of the silicon nano power body that embodiment 4 obtains;
Fig. 7 is the x-ray diffractogram of the silicon nano power body that embodiment 5 obtains;
Fig. 8 is the x-ray diffractogram of the silicon nano power body that embodiment 6 obtains;
Fig. 9 is the feature charging and discharging curve figure of the silicon nano power body that embodiment 1 obtains;
Figure 10 is the low range electrochemical cycle stability figure of the silicon nano power body that embodiment 1 obtains;
Figure 11 is the high rate cyclic stability diagram of the nano-silicon powder that embodiment 1 obtains.
Embodiment
Carry out clear below in conjunction with embodiment to technical scheme of the present invention, detailed description.But should be appreciated that described embodiment is only a part of the present invention, instead of whole embodiment.Based on the embodiment in the present invention, the technical work personnel of this area are not making the every other embodiment obtained under creative work prerequisite.All belong to protection scope of the present invention.
The chemical reagent adopted in the embodiment of the present invention is market and buys, and wherein magnesium powder, aluminum trichloride (anhydrous), hydrochloric acid and hydrofluoric acid are bought in chemical reagents corporation of traditional Chinese medicines group, and silicon tetrachloride is bought in An Naiji chemical reagents corporation.
The invention discloses preparation method and the application thereof of magnanimity synthesis silicon nano material in a kind of molten salt system, comprising:
Embodiment 1: silicon tetrachloride be raw material in Aluminum chloride anhydrous molten salt system 200 DEG C prepare silicon nano material.
Get 2mL silicon tetrachloride, after 0.82 magnesium powder mixes with 5.0g aluminum trichloride (anhydrous), put into 20mL stainless steel autoclave, seal and be placed in electrical crucible, in 200 DEG C, reacting 10h respectively, then naturally cool to room temperature; After driving still, products therefrom is through washing, 1M dilute hydrochloric acid cleaning also centrifugation, and gained solid adopts diluted hydrofluoric acid to carry out short period of time immersion, then washes centrifugal drying further, namely obtains pure phase silicon nano power body.
Adopt X light powder diffraction instrument to carry out X light diffracting analysis, Fig. 1 is the x-ray diffraction spectra of this embodiment gained powder.As seen from the figure, in x-ray diffraction spectra, 2 θ have apparent 5 diffraction peaks within the scope of 10-80 °, and all diffraction peaks can index be all the Si (JPCDS 77-2111) of Emission in Cubic.Program productive rate is ~ 70%.
It is nano level small-particle composition that the scanning electron microscope (SEM) photograph (Fig. 2) of product and transmission electron microscope picture (Fig. 3) show silica flour prepared by this condition.
Embodiment 2: scheme as described in Example 1, adjustment temperature of reaction is 300 DEG C, prepares nano silicone powder.Crystallinity gets a promotion.Fig. 4 is the x-ray diffraction spectra of this embodiment gained powder.It is pure silicon phase (JPCDS 77-2111) that spectrogram shows this powder.
Embodiment 3: scheme as described in Example 1, adjustment temperature of reaction is 400 DEG C, prepares nano silicone powder.Crystallinity is promoted further.Fig. 5 is the x-ray diffraction spectra of this embodiment gained powder.It is pure silicon phase (JPCDS 77-2111) that spectrogram shows this powder.
Embodiment 4: scheme as described in Example 1, adjustment metal magnesium powder is sodium Metal 99.5, prepares nano silicone powder.Fig. 6 is the x-ray diffraction spectra of this embodiment gained powder.It is pure silicon phase (JPCDS 77-2111) that spectrogram shows this powder.
Embodiment 5: as described in Example 2 scheme, adjustment Aluminum chloride anhydrous fused salt is Aluminum chloride anhydrous with Zinc Chloride Anhydrous by the quality of 1:1 than fused salt mixt, prepares nano silicone powder.Fig. 7 is the x-ray diffraction spectra of this embodiment gained powder.It is pure silicon phase (JPCDS77-2111) that spectrogram shows this powder.
Embodiment 6: as described in Example 2 scheme, adjustment Aluminum chloride anhydrous fused salt is Aluminum chloride anhydrous with Magnesium Chloride Anhydrous by the quality of 1:1 than fused salt mixt, prepares nano silicone powder.Fig. 8 is the x-ray diffraction spectra of this embodiment gained powder.It is pure silicon phase (JPCDS77-2111) that spectrogram shows this powder.
The product of above-described embodiment 1 is dressed up CR2016 button cell, be for barrier film to electrode polyolefin porous membrane (Celgard 2500) with lithium sheet, using the mixing solutions of the NSC 11801 of LiPF6 (EC) and methylcarbonate (DMC) (volume ratio 1:1) as electrolytic solution, (Sai Wei Electron Material Co., Ltd of Zhuhai City) CR2016 battery completes in the glove box of argon gas atmosphere.Silicon electrode adopts the Xylo-Mucine sizing agent (traditional Chinese medicines chemical reagent company limited) of the silicon nano power body in the embodiment of 70wt%, 10wt%, graphitized carbon black, the water of 20% mixes, and the substrate of electrode film is metal copper foil.Electric performance test is carried out at probe temperature is 25 DEG C.Fig. 9-11 is the electrochemical lithium storage performance map of the silicon nano power body of above-described embodiment gained.As seen from Figure 9, the specific storage of first charge-discharge is respectively 3549 and 4189mAh/g, and corresponding first circle efficiency for charge-discharge reaches 84.7%.Drawn by Figure 10, carry out constant current charge-discharge when current density is 1.2A/g, after 50 circles, reversible specific capacity can remain to 3083mAh/g.Found out by Figure 11, when current density is 3A/g, after circulation 300 circle, reversible specific capacity still can reach 1380mAh/g.
Embodiment result shows, the present invention in low-temperature molten salt system, can use cheap silicon tetrachloride etc. to be raw material, realize the preparation of silicon nano power body.By controlling reactant ratio, temperature of reaction, the factors such as fused salt, improve the crystallinity of product.When this material is used for lithium ion battery negative material, demonstrates the lithium storage content far above graphite cathode and good cyclical stability, can be used as potential high performance lithium ionic cell cathode material of future generation.
Claims (10)
1. prepare a method for silicon nano power, under described method is included in the fused salt condition of 200 DEG C ~ 500 DEG C, with metallic reducing silicon tetrachloride to synthesize the step of silicon nano power.
2. method according to claim 1, described metal is selected from sodium Metal 99.5, magnesium powder, the one in aluminium powder or several, or its corresponding metal alloy.
3. method according to claim 1, described fused salt is selected from Aluminum chloride anhydrous, Zinc Chloride Anhydrous, Magnesium Chloride Anhydrous, one or several in anhydrous chlorides of rase sodium.
4. method according to claim 1, the reaction times of described reduction is 5 hours to 3 days, is preferably 5-20 hour.
5. method according to claim 1, the temperature of reaction of described reduction is 200 DEG C ~ 400 DEG C.
6. method according to claim 1, described method also comprises washing, pickling, hydrofluoric acid dips removing impurity and the step of filtration drying after reduction reaction.
7. method according to claim 1, described reduction is carried out in stainless steel cauldron.
8. method according to claim 1, described silicon nano power is unbodied nano-scale particle.
9. a silicon nano power, described silicon nano power is prepared by the method described in any one of 1-8.
10. silicon nano power according to claim 9 is used for the purposes of lithium cell cathode material.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084365A (en) * | 2015-07-17 | 2015-11-25 | 中国科学技术大学 | Preparation method for silicon nano material and application |
| CN106299284A (en) * | 2016-09-07 | 2017-01-04 | 扬州大学 | A kind of low temperature preparation method of hole, attapulgite Quito silicon nanowires |
| CN106384818A (en) * | 2016-09-07 | 2017-02-08 | 扬州大学 | Low-temperature preparation method of open-mesopore hollow silicon nanospheres |
| CN107195904A (en) * | 2017-04-06 | 2017-09-22 | 中国计量大学 | A kind of silicon electrode material preparation method of core shell structure |
| CN110386604A (en) * | 2019-08-09 | 2019-10-29 | 北方奥钛纳米技术有限公司 | The preparation method of nano-silicon, silicon based anode material and preparation method thereof |
| CN110540207A (en) * | 2019-09-18 | 2019-12-06 | 上海应用技术大学 | method for preparing high-purity nano silicon material by using industrial waste |
| CN110713187A (en) * | 2019-09-23 | 2020-01-21 | 北京化工大学 | Preparation method of silicon material and application of silicon material in lithium ion battery cathode |
| CN111193013A (en) * | 2020-01-08 | 2020-05-22 | 青岛泰达华润新能源科技有限公司 | Preparation method of silicon-carbon negative electrode material for lithium ion battery |
| CN115215340A (en) * | 2021-04-19 | 2022-10-21 | 四川物科金硅新材料科技有限责任公司 | Nano silicon wire and preparation method thereof |
| CN115231554A (en) * | 2022-07-15 | 2022-10-25 | 哈尔滨工程大学 | Preparation method of self-synthesized nano silicon-carbon composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679043A (en) * | 2007-04-02 | 2010-03-24 | 诺尔斯海德公司 | A method and a reactor for production of high-purity silicon |
| WO2011078225A1 (en) * | 2009-12-22 | 2011-06-30 | Jnc株式会社 | Method for manufacturing polysilicon and method for manufacturing silicon tetrachloride |
| CN102161488A (en) * | 2011-02-28 | 2011-08-24 | 中南大学 | Method for preparing solar-grade polysilicon |
| CN103904307A (en) * | 2012-12-24 | 2014-07-02 | 宁波杉杉新材料科技有限公司 | Silicon-carbon composite material, preparation method and application thereof |
-
2014
- 2014-12-03 CN CN201410729242.4A patent/CN104528728A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679043A (en) * | 2007-04-02 | 2010-03-24 | 诺尔斯海德公司 | A method and a reactor for production of high-purity silicon |
| WO2011078225A1 (en) * | 2009-12-22 | 2011-06-30 | Jnc株式会社 | Method for manufacturing polysilicon and method for manufacturing silicon tetrachloride |
| CN102161488A (en) * | 2011-02-28 | 2011-08-24 | 中南大学 | Method for preparing solar-grade polysilicon |
| CN103904307A (en) * | 2012-12-24 | 2014-07-02 | 宁波杉杉新材料科技有限公司 | Silicon-carbon composite material, preparation method and application thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084365A (en) * | 2015-07-17 | 2015-11-25 | 中国科学技术大学 | Preparation method for silicon nano material and application |
| CN106299284A (en) * | 2016-09-07 | 2017-01-04 | 扬州大学 | A kind of low temperature preparation method of hole, attapulgite Quito silicon nanowires |
| CN106384818A (en) * | 2016-09-07 | 2017-02-08 | 扬州大学 | Low-temperature preparation method of open-mesopore hollow silicon nanospheres |
| CN107195904A (en) * | 2017-04-06 | 2017-09-22 | 中国计量大学 | A kind of silicon electrode material preparation method of core shell structure |
| CN107195904B (en) * | 2017-04-06 | 2019-09-20 | 中国计量大学 | A kind of silicon electrode material preparation method of core-shell structure |
| CN110386604A (en) * | 2019-08-09 | 2019-10-29 | 北方奥钛纳米技术有限公司 | The preparation method of nano-silicon, silicon based anode material and preparation method thereof |
| CN110540207A (en) * | 2019-09-18 | 2019-12-06 | 上海应用技术大学 | method for preparing high-purity nano silicon material by using industrial waste |
| CN110540207B (en) * | 2019-09-18 | 2023-02-10 | 上海应用技术大学 | Method for preparing high-purity nano silicon material by using industrial waste |
| CN110713187A (en) * | 2019-09-23 | 2020-01-21 | 北京化工大学 | Preparation method of silicon material and application of silicon material in lithium ion battery cathode |
| CN111193013A (en) * | 2020-01-08 | 2020-05-22 | 青岛泰达华润新能源科技有限公司 | Preparation method of silicon-carbon negative electrode material for lithium ion battery |
| CN115215340A (en) * | 2021-04-19 | 2022-10-21 | 四川物科金硅新材料科技有限责任公司 | Nano silicon wire and preparation method thereof |
| CN115231554A (en) * | 2022-07-15 | 2022-10-25 | 哈尔滨工程大学 | Preparation method of self-synthesized nano silicon-carbon composite material |
| CN115231554B (en) * | 2022-07-15 | 2023-12-29 | 哈尔滨工程大学 | Preparation method of self-synthesized nano silicon-carbon composite material |
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