CN102167399A - Preparation method of bowknot-shaped antimonous oxide - Google Patents
Preparation method of bowknot-shaped antimonous oxide Download PDFInfo
- Publication number
- CN102167399A CN102167399A CN 201110132815 CN201110132815A CN102167399A CN 102167399 A CN102167399 A CN 102167399A CN 201110132815 CN201110132815 CN 201110132815 CN 201110132815 A CN201110132815 A CN 201110132815A CN 102167399 A CN102167399 A CN 102167399A
- Authority
- CN
- China
- Prior art keywords
- preparation
- antimonous oxide
- bow tie
- antimonous
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000012265 solid product Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000013543 active substance Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical class [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of bowknot-shaped antimonous oxide. The preparation method comprises the following steps of: dissolving a raw material, i.e. a trivalent antimony salt, in an ethanol-deionized water mixing solvent according to a volume ratio of 1: 1-1: 3 to prepare 0.01-0.1mol/L of solution; adding a surfactant to the solution, adding an alkaline regulator to regulate the pH value to be 8-12, then reacting for 1-24h at 100-250 DEG C in a sealed environment and naturally cooling to the room temperature; and collecting a reaction product, alternately washing and drying the solid product through deionized water and absolute ethyl alcohol to obtain the bowknot-shaped antimonous oxide. The preparation method disclosed by the invention is simple and controllable, has short period and low cost and is beneficial to large-scale industrial production; and the obtained product has high purity and uniformly-distributed particle sizes and is of a bowknot shape because two ends of the particle are split.
Description
Technical field
The present invention relates to the lithium ion battery field of compound material, be specifically related to a kind of preparation method of bow tie antimonous oxide.
Background technology
Lithium ion battery has advantages such as operating voltage height, energy density is big, safety performance is good, therefore in portable type electronic products such as digital camera, mobile telephone and notebook computer, be used widely, also have application prospect for electric bicycle and electromobile.The negative material of present commercial lithium ion battery is the carbon material of graphite and other form.Because the theoretical capacity of graphite has only 372mAhg
-1, and embedding lithium current potential is lower, has limited its use range.
Compare with more traditional carbon material, some metal oxide has higher lithium storage content, as Sb
2O
3Lithium storage content reach 550mAhg
-1, far above carbon material.Though easily prepare Sb with traditional hydrolysis method
2O
3, but because Sb
3+Easily hydrolysis fast, gained Sb
2O
3Size is bigger, is difficult to the tiny Sb of preparation particle
2O
3Particle.And oarse-grained Sb
2O
3Because volume change is bigger, electrochemical stability is relatively poor as lithium ion battery negative material.
Therefore, be necessary to develop and a kind ofly can access the Sb that is applicable to lithium ion battery negative material
2O
3The preparation method.
Summary of the invention
The invention provides a kind of preparation method of bow tie antimonous oxide, this method technology is simple, and cost is low, is suitable for large-scale industrial production.
The present invention also provides a kind of bow tie antimonous oxide, and this structure is significant for the chemical property that improves this material.
A kind of preparation method of bow tie antimonous oxide comprises step:
1), be raw material with the antimonous salt, it is in ethanol-deionized water mixed solvent of 1: 1～1: 3 that raw material is dissolved in ethanol and deionized water volume ratio, is mixed with the solution that antimonous salt concentration is 0.01mol/L～0.1mol/L;
2), will add tensio-active agent in the solution, add alkaline conditioner again the pH value transferred to 8～12, then in sealed environment in 100 ℃～250 ℃ reactions 1 hour～24 hours, naturally cool to room temperature then;
3), collecting reaction product, through the washing of deionized water and dehydrated alcohol alternate repetition, drying obtains the bow tie antimonous oxide with solid product.
In order to reach better invention effect, preferably:
In the step 1), described antimonous salt is selected antimonious muriate, antimonious nitrate, antimonious vitriol, antimonious oxalate or antimonious acetate for use.
Step 2) in, described tensio-active agent can be selected this area tensio-active agent commonly used for use, preferred cetyl trimethylammonium bromide (CTAB), sodium laurylsulfonate (SDS) or polyvinylpyrrolidone (PVP) etc.
The mol ratio of described tensio-active agent and antimonous salt is 0.01: 1～1: 1.
Described alkaline conditioner can be selected this area alkaline conditioner commonly used for use, preferred ammoniacal liquor, aqueous sodium hydroxide solution or potassium hydroxide aqueous solution etc.The qualification that the concentration of alkaline conditioner is not strict, be as the criterion with convenient the adjusting, generally selecting low concentration solution for use, is 10%～30% ammoniacal liquor, 2mol/L～10mol/L aqueous sodium hydroxide solution or 2mol/L～10mol/L potassium hydroxide aqueous solution etc. as selecting concentration expressed in percentage by weight for use.
The present invention has the following advantages:
1, the present invention adopts solvent thermal to prepare the method for antimonous oxide, and technology is simple and controlled, the cycle is short, cost is low, helps large-scale industrial production.
, products therefrom purity height, particle size distribution be even, particle two ends cracking is bow tie, this structure is equivalent to reduce Sb
2O
3The particulate size has not only enlarged Sb
2O
3The particulate specific surface area with and and the contact area of electrolytic solution, and shortened the diffusion length of lithium ion in particle, significant for the chemical property that improves this material, will have a broad prospect of the use at tool aspect catalysis, photoelectricity and the electrochemical lithium storage.
Description of drawings
Fig. 1 is embodiment 1 gained Sb
2O
3The X-ray diffraction in crystals collection of illustrative plates.
Fig. 2 is embodiment 1 gained Sb
2O
3The crystalline stereoscan photograph.
Fig. 3 is embodiment 2 gained Sb
2O
3The X-ray diffraction in crystals collection of illustrative plates.
Fig. 4 is embodiment 2 gained Sb
2O
3The crystalline stereoscan photograph.
Fig. 5 is embodiment 3 gained Sb
2O
3The X-ray diffraction in crystals collection of illustrative plates.
Fig. 6 is embodiment 3 gained Sb
2O
3The crystalline stereoscan photograph.
Fig. 7 is embodiment 4 gained Sb
2O
3The X-ray diffraction in crystals collection of illustrative plates.
Fig. 8 is embodiment 4 gained Sb
2O
3The crystalline stereoscan photograph.
Embodiment
Embodiment 1
1), with SbCl
3Be raw material, with SbCl
3Be dissolved in ethanol and deionized water volume ratio and be in ethanol-deionized water mixed solvent of 1: 1, be mixed with SbCl
3Concentration is the solution of 0.05mol/L;
2), solution is placed autoclave, adding Surfactant CTAB, CTAB and SbCl
3Mol ratio be 0.01: 1, use the ammoniacal liquor of 25wt% (weight percent) that the pH value is transferred to 9 again, then with reactor sealing,, naturally cool to room temperature then 160 ℃ of reactions 4 hours down;
3), collecting reaction product, through the washing of deionized water and dehydrated alcohol alternate repetition, drying obtains final reacting product bow tie antimonous oxide with solid product.
Adopt RigakuD/MAX-2550PC type X ray polycrystalline diffractometer that the final reacting product of gained is carried out material phase analysis, X ray diffracting spectrum (XRD figure spectrum) is as Fig. 1, as can be seen from Figure 1: all diffraction peaks all can be classified as Sb
2O
3
Adopt scanning electron microscope that the final reacting product of gained is analyzed, its stereoscan photograph such as Fig. 2, as can be seen from Figure 2: the product that obtains is bow tie Sb
2O
3, be of a size of 10 μ m-15 μ m.
Embodiment 2
1), with Sb (NO
3)
3Be raw material, with Sb (NO
3)
3Be dissolved in ethanol and deionized water volume ratio and be in ethanol-deionized water mixed solvent of 1: 2, be mixed with SbCl
3Concentration is the solution of 0.01mol/L;
2), solution is placed autoclave, adding surfactant SDS, SDS and SbCl
3Mol ratio be 0.5: 1, use the NaOH aqueous solution of 6M (mol/L) that the pH value is transferred to 10 again, then with reactor sealing,, naturally cool to room temperature then 180 ℃ of reactions 8 hours down;
3), collecting reaction product, through the washing of deionized water and dehydrated alcohol alternate repetition, drying obtains final reacting product bow tie antimonous oxide with solid product.
Adopt RigakuD/MAX-2550PC type X ray polycrystalline diffractometer that the final reacting product of gained is carried out material phase analysis, the XRD figure spectrum shows as Fig. 3: all diffraction peaks all can be classified as Sb
2O
3
Adopt scanning electron microscope that the final reacting product of gained is analyzed, its stereoscan photograph such as Fig. 4 show: the product that obtains is bow tie Sb
2O
3, be of a size of 10-15 μ m.
Embodiment 3
1), with Sb (CH
3COO)
3Be raw material, with Sb (CH
3COO)
3Be dissolved in ethanol and deionized water volume ratio and be in ethanol-deionized water mixed solvent of 1: 3, be mixed with SbCl
3Concentration is the solution of 0.075mol/L;
2), solution is placed autoclave, adding tensio-active agent PVP (Chemical Reagent Co., Ltd., Sinopharm Group, molecular weight is about 5800), PVP and Sb (CH
3COO)
3Mol ratio be 1: 1, the ammoniacal liquor with 25wt% transfers to 11 with the pH value again, then with reactor sealing, 200 ℃ of reactions 2 hours down, naturally cools to room temperature then;
3), collecting reaction product, through the washing of deionized water and dehydrated alcohol alternate repetition, drying obtains final reacting product bow tie antimonous oxide with solid product.
Adopt RigakuD/MAX-2550PC type X ray polycrystalline diffractometer that the final reacting product of gained is carried out material phase analysis, the XRD figure spectrum shows as Fig. 5: all diffraction peaks all can be classified as Sb
2O
3
Adopt scanning electron microscope that the final reacting product of gained is analyzed, its stereoscan photograph such as Fig. 6 show: the product that obtains is bow tie Sb
2O
3, be of a size of 10-15 μ m.
Embodiment 4
1), with SbCl
3Be raw material, with SbCl
3Be dissolved in ethanol and deionized water volume ratio and be in ethanol-deionized water mixed solvent of 1: 1, be mixed with SbCl
3Concentration is the solution of 0.1mol/L;
2), solution is placed autoclave, adding surfactant SDS, SDS and SbCl
3Mol ratio be 1: 1, the ammoniacal liquor with 25wt% transfers to 10 with the pH value again, then with reactor sealing, 200 ℃ of reactions 2 hours down, naturally cools to room temperature then;
3), collecting reaction product, through the washing of deionized water and dehydrated alcohol alternate repetition, drying obtains final reacting product bow tie antimonous oxide with solid product.
Adopt RigakuD/MAX-2550PC type X ray polycrystalline diffractometer that the final reacting product of gained is carried out material phase analysis, the XRD figure spectrum shows as Fig. 7: all diffraction peaks all can be classified as Sb
2O
3
Adopt scanning electron microscope that the final reacting product of gained is analyzed, its stereoscan photograph such as Fig. 8 show: the product that obtains is bow tie Sb
2O
3, be of a size of 10-15 μ m.
Claims (7)
1. the preparation method of a bow tie antimonous oxide is characterized in that, comprises step:
1), be raw material with the antimonous salt, it is in ethanol-deionized water mixed solvent of 1: 1～1: 3 that raw material is dissolved in ethanol and deionized water volume ratio, is mixed with the solution that antimonous salt concentration is 0.01mol/L～0.1mol/L;
2), will add tensio-active agent in the solution, add alkaline conditioner again the pH value transferred to 8～12, then in sealed environment in 100 ℃～250 ℃ reactions 1 hour～24 hours, naturally cool to room temperature then;
3), collecting reaction product, through the washing of deionized water and dehydrated alcohol alternate repetition, drying obtains the bow tie antimonous oxide with solid product.
2. the preparation method of bow tie antimonous oxide according to claim 1, it is characterized in that, in the step 1), described antimonous salt is antimonious muriate, antimonious nitrate, antimonious vitriol, antimonious oxalate or antimonious acetate.
3. the preparation method of bow tie antimonous oxide according to claim 1 is characterized in that step 2) in, described tensio-active agent is cetyl trimethylammonium bromide, sodium laurylsulfonate or polyvinylpyrrolidone.
4. the preparation method of bow tie antimonous oxide according to claim 1 is characterized in that step 2) in, the mol ratio of described tensio-active agent and antimonous salt is 0.01～1: 1.
5. the preparation method of bow tie antimonous oxide according to claim 1 is characterized in that step 2) in, described alkaline conditioner is ammoniacal liquor, aqueous sodium hydroxide solution or potassium hydroxide aqueous solution.
6. the preparation method of bow tie antimonous oxide according to claim 5, it is characterized in that, step 2) in, described alkaline conditioner is that concentration expressed in percentage by weight is 10%～30% ammoniacal liquor, 2mol/L～10mol/L aqueous sodium hydroxide solution or 2mol/L～10mol/L potassium hydroxide aqueous solution.
7. according to the bow tie antimonous oxide of the preparation method of each described bow tie antimonous oxide of claim 1～6 preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101328151A CN102167399B (en) | 2011-05-20 | 2011-05-20 | Preparation method of bowknot-shaped antimonous oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101328151A CN102167399B (en) | 2011-05-20 | 2011-05-20 | Preparation method of bowknot-shaped antimonous oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102167399A true CN102167399A (en) | 2011-08-31 |
| CN102167399B CN102167399B (en) | 2012-08-22 |
Family
ID=44488754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101328151A Expired - Fee Related CN102167399B (en) | 2011-05-20 | 2011-05-20 | Preparation method of bowknot-shaped antimonous oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102167399B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502819A (en) * | 2011-11-02 | 2012-06-20 | 宁波大学 | Preparation method of lithium ion battery PbSbO2Cl cathode material |
| CN105938922A (en) * | 2016-06-28 | 2016-09-14 | 陕西科技大学 | Preparation method of dumbbell-shaped negative electrode material for sodium-ion battery |
| CN106252632A (en) * | 2016-09-18 | 2016-12-21 | 陕西科技大学 | A kind of carbon fiber and the preparation method of stibium oxide composite |
| CN108706633A (en) * | 2018-05-22 | 2018-10-26 | 湖南工业大学 | A kind of antimony oxide and preparation method thereof applied to lithium ion battery negative material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519225A (en) * | 2009-03-26 | 2009-09-02 | 上海大学 | Method for preparing ordered antimony-based oxide self-assembled nanometer cluster and nano-wire materials |
-
2011
- 2011-05-20 CN CN2011101328151A patent/CN102167399B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519225A (en) * | 2009-03-26 | 2009-09-02 | 上海大学 | Method for preparing ordered antimony-based oxide self-assembled nanometer cluster and nano-wire materials |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502819A (en) * | 2011-11-02 | 2012-06-20 | 宁波大学 | Preparation method of lithium ion battery PbSbO2Cl cathode material |
| CN102502819B (en) * | 2011-11-02 | 2014-01-29 | 宁波大学 | Preparation method of lithium ion battery PbSbO2Cl cathode material |
| CN105938922A (en) * | 2016-06-28 | 2016-09-14 | 陕西科技大学 | Preparation method of dumbbell-shaped negative electrode material for sodium-ion battery |
| CN106252632A (en) * | 2016-09-18 | 2016-12-21 | 陕西科技大学 | A kind of carbon fiber and the preparation method of stibium oxide composite |
| CN108706633A (en) * | 2018-05-22 | 2018-10-26 | 湖南工业大学 | A kind of antimony oxide and preparation method thereof applied to lithium ion battery negative material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102167399B (en) | 2012-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Or et al. | Recycling of mixed cathode lithium‐ion batteries for electric vehicles: Current status and future outlook | |
| Zhang et al. | Innovative application of acid leaching to regenerate Li (Ni1/3Co1/3Mn1/3) O2 cathodes from spent lithium-ion batteries | |
| Deng et al. | Direct recovery and efficient reutilization of degraded ternary cathode materials from spent lithium-ion batteries via a homogeneous thermochemical process | |
| Sun et al. | Synthesis and adsorption properties of Li1. 6Mn1. 6O4 by a combination of redox precipitation and solid-phase reaction | |
| CN102185143A (en) | Transition metal oxide/ graphene composite material and preparation method thereof | |
| CN103311505B (en) | A kind of preparation method of graphene-ternary composite positive electrode material for lithium ion battery | |
| CN102760885B (en) | Tin-base complex oxide/graphene composite material, and preparation method and application thereof | |
| CN102231436B (en) | Preparation method of Sn-Sb/grapheme nano-composite material | |
| CN102315433A (en) | Graphene loaded Cu-CuxO composite material and preparation method thereof | |
| CN103151506A (en) | Preparation method of nanoscale zirconium-doped lithium titanate material | |
| CN102760871A (en) | Metallic antimony/graphene composite material, and preparation method and application thereof | |
| CN103107313B (en) | Tin-based oxide/graphene composite material,preparation method and application thereof | |
| CN112062167B (en) | Micron-sized binary doped lithium-rich material and preparation method and application thereof | |
| CN103151508A (en) | Lanthanum lithium titanate doped composite negative electrode material of lithium ion battery and preparation method thereof | |
| CN104993104A (en) | Preparation method of multi-element polyphase composite lithium ion battery negative material | |
| CN104528728A (en) | Method for synthesizing nano-silicon powder by using silicon tetrachloride as raw material and application of nano-silicon powder | |
| Liu et al. | Synthesis of Ni-Rich cathode material from maleic acid-leachate of spent lithium-ion batteries | |
| CN102167399B (en) | Preparation method of bowknot-shaped antimonous oxide | |
| Huang et al. | Enhancing the electrocatalysis of LiNi0. 5Co0. 2Mn0. 3O2 by introducing lithium deficiency for oxygen evolution reaction | |
| Cai et al. | Engineering Electrolytic Silicon–Carbon Composites by Tuning the In Situ Magnesium Oxide Space Holder: Molten-Salt Electrolysis of Carbon-Encapsulated Magnesium Silicates for Preparing Lithium-Ion Battery Anodes | |
| Bai et al. | Clean universal solid-state recovery method of waste lithium-ion battery ternary positive materials and their electrochemical properties | |
| CN104986768A (en) | Method for synthesizing silicon nanopowder through nitridation, and application thereof | |
| CN106410185B (en) | A kind of preparation method of the Manganese Based Cathode Materials for Lithium Ion Batteries of yolk-eggshell structure | |
| CN103107323A (en) | Cerium-doped modified lithium titanate negative material of lithium ion secondary battery and preparation method thereof | |
| CN109671937B (en) | In-situ synthesis method of transition metal oxide/graphene composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120822 Termination date: 20150520 |
|
| EXPY | Termination of patent right or utility model |