CN102694173A - Hydrothermal synthesis method for nanowire/stick-like morphology manganese lithium silicate - Google Patents
Hydrothermal synthesis method for nanowire/stick-like morphology manganese lithium silicate Download PDFInfo
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Abstract
The invention discloses an organic additive assisted hydrothermal synthesis method for one-dimensional nanometre morphology manganese lithium silicate anode material, belonging to the technical field of electrochemical electrical source materials. In the method, cheap organic additives including polyvinyl alcohol (PVA) and ascorbic acid (VC) are adopted as morphology guide modulators, so that an one-dimensional nanometre morphology manganese lithium silicate anode material is directly acquired by combining a simple and easy soft template synthesis method with the hydrothermal synthesis method; simultaneously, a carbon source is in-situ introduced, and a calcining technology is further adopted to in-situ generate an Li2MnSiO4/C composite anode material, so that the electrochemical performance of the electrode is greatly improved. Relative to a solid-phase method and a sol-gel method, a pure phase can be acquired easily, and battery charging and discharging performance of the electrode is greatly improved. Besides, the synthesis method provides a method for preparing manganese lithium silicate one-dimensional nanometre anode material and has a wide application prospect in the lithium-ion battery anode material.
Description
Technical field
The invention belongs to the electrochemical power source technical field of material, relate in particular to a kind of hydrothermal synthesis method that in adding the organic environment that crystal growth is played special guide effect, prepares nano wire/bar-shaped pattern anode material for lithium ion battery manganese silicate of lithium.
Background technology
In the nano material of various forms; The preparation of monodimension nanometer material and special appearance nano material is that nano material obtains key in application at aspects such as nano-device, catalyst and transducers; Since the eighties in 20th century; The material of zero dimension has been obtained very big progress, but the preparation of monodimension nanometer material still is faced with great challenge with research, will become the major fields of nano materials research from now in quite over a long time.
The synthesizing one-dimensional nano material mainly contains following several kinds of thinkings: (1) utilizes the anisotropic crystal structure of solid itself to realize one-dimensional growth; (2) introduce the symmetry that liquid-solid interface reduces crystal seed; (3) guide the formation of one-dimensional nano structure with various templates with one dimension pattern; (4) through controlling the habit that degree of supersaturation changes crystal seed; (5) with the speed of growth of suitable capping reagent (coating agent) from the different crystal faces of dynamics angle control crystal seed; (6) realize the formation of one-dimensional nano structure through the self assembly of zero-dimension nano structure; (7) size of reduction micro-structural, or the like.Wherein template synthesizing one-dimensional nano material has universality, and is extensively adopted.Template is divided into " hard template method " and " soft template method ".
Hard template is at present normal, and what use is foraminous die plate, and like anodised aluminium, zeolite molecular sieve, CNT etc., it is that method with electrochemical deposition prepares monodimension nanometer material that foraminous die plate uses maximum.Zhou etc. are with poroid pellumina (AAO) template and LiAC and Mn (AC)
2The mixed solution effect, dry back and sintering promptly get the LiMn that is deposited in the hole
2O
4Nanometer rods is removed the LiMn that template obtains diameter 200nm with NaOH
2O
4Nanometer rods (Ying-ke Zhou, Cheng-min Shen, Jier Huang, Hu-lin Li.Synthesis of high-ordered LiMn
2O
4Nanowire arrays by AAO template and its structural properties.Materials Science and Engineering B-Solid State Materials for Advanced Technology; 2002,95:77-82).Liu etc. are with LiNO
3, FeSO
4, ammonium dihydrogen phosphate and citric acid be raw material, sol-gel process and porous AAO template are compound, obtain LiFePO
4One-dimensional nano-array (Xiao-hong Liu, Jin-qing Wang, Jun-yan Zhang, Sheng-rong Yang.Fabrication and characterization of LiFePO
4Nanotubes by a sol-gel-AAO template process.Chinese Journal of Chemical Physics, 2006,19 (6): 530-534).Therefore the synthetic physicochemical properties that are subject to template itself and institute's synthetic of hard template method lack variation.And because the aperture of template is all bigger, the material that synthesizes often all has bigger size.
Soft template mainly contains surfactant templates and biological macromolecular template.Surfactant such as polybutene alcohol (PVB), polyacrylamide (PAM), PVP (PVP), neopelex (SDBS) etc. are as under the template action; Through the technological parameters such as concentration of control surface activating agent, can make one dimension polycrystalline Nano material.But the research that is used for anode material for lithium-ion batteries does not also appear in the newspapers.
Recently, found and LiFePO
4The Li of isomorphism
2MSiO
4(M=Mn, Fe, Co, Ni) serial novel silicon hydrochlorate base anode material, the characteristic that can have two lithium ions to deviate to have higher specific energy, raw material ABUNDANT NATUREAL RESOURSES and environmental friendliness etc. in theory owing to them begins to cause people's attention.Li
2MnSiO
4Easily synthetic pure phase has high theoretical voltage platform 4.1V, with LiCoO
2Voltage platform (3.9～4.0V) quite, is fit to present battery system, possibly be to substitute LiCoO in the future
2Cheap mgag electrode material.Milke etc. are with lithium acetate, manganese acetate and SiO
2Being raw material, is solvent with water, 200 ℃ of following hydro-thermal reactions 3 days, but the hydrothermal product that obtains is nanometer spherical shape pattern (Bettina Milke, Peter Strauch, Markus Antonietti, Cristina Giordano.Synthesis of Li
yMnSiO
xAnd LiMnPO
4Nanostructures.Nanoscale, 2009,1:110-113).Muraliganth etc. are with LiOHH
2O, manganese acetate and tetraethoxysilane are raw material, are solvent with ethylene glycol, the reaction 20 minutes down of 300 ℃ of microwave-assisted hydro-thermals, and the hydrothermal product that obtains is calcined 6h with after sucrose mixes for 650 ℃ in argon gas atmosphere, but that obtain is nanoparticle agglomerates pattern Li
2MnSiO
4(T.Muraliganth, K.R.Stroukoff, A.Manthiram.Microwave-Solvothermal Synthesis of Nanostructured Li
2MSiO
4/ C (M=Mn and Fe) Cathodes for Lithium-Ion Batteries.Chem.Mater.2010,22:5754-576).Aravindan etc. are with LiOHH
2O, MnCl
24H
2O and SiO
2Be raw material, be mixed into solvent with water and ethylene glycol, 150 ℃ of following hydro-thermal reaction 48h, the hydrothermal product that obtains is with after adipic acid mixes, and 700 ℃ of calcinings obtain Li in argon gas atmosphere
2MnSiO
4, but that obtain is floriform appearance (V Aravindan, K Karthikeyan, J W Lee, S Madhavi, Y S Lee.Synthesis and improved electrochemical properties of Li
2MnSiO
4Cathodes, J.Phys.D:Appl.Phys.2011,44:152001).
Template has good controllability, can effectively control the structure of gained material, is one of key technology of preparation special appearance material.Hydro thermal method can the synthesis nano lithium ion battery material, and prepared nano cell material has shortened the ions diffusion path, has bigger specific area, helps increasing the embedding lithium capacity and the multiplying power property of electrode.Hydro thermal method combines template to prepare special appearance nanoscale Li
2MnSiO
4Positive electrode does not also appear in the newspapers.
Summary of the invention
The purpose of this invention is to provide a kind of hydrothermal synthesis method for preparing nano wire/bar-shaped pattern anode material for lithium ion battery manganese silicate of lithium.Purpose is to disclose a kind of hydrothermal synthesis method that in the thermal and hydric environment that adds organic substance polyvinyl alcohol (PVA) or ascorbic acid (VC), prepares nano wire/bar-shaped anode material for lithium ion battery manganese silicate of lithium.
A kind of hydrothermal synthesis method for preparing nano wire/bar-shaped anode material for lithium ion battery manganese silicate of lithium; It is characterized in that; In raw material, add organic substance polyvinyl alcohol (PVA), ascorbic acid (VC); Prepare the hydrothermal synthesis method of nano wire/bar-shaped manganese silicate of lithium as directed agents, its concrete steps are:
With Lithium hydroxide monohydrate, four water manganese acetates, tetraethoxysilane is parent stock according to x: 1: 1 (2≤x≤8) mole proportioning takes by weighing and is dissolved in the deionized water of certain volume amount; Be placed in the ball grinder; The organics additive that adds the certain mass mark; With 150～200 rev/mins rotating speed ball millings 10 minutes; Pour into and have in the teflon-lined stainless steel cauldron, after the sealing agitated reactor is put into rotatable homogeneous reactor with 10～30 rev/mins rotating speed, at 150 ℃～220 ℃ following hydro-thermal reaction 24～72h.Take out agitated reactor after reaction is accomplished, be cooled to room temperature, take out product.Wash, filter, after the drying, promptly obtain Li with deionized water and alcohol
2MnSiO
41-dimention nano positive electrode powder, further under high pure nitrogen, argon gas atmosphere, the calcination processing 5～10h through 500～800 ℃ obtains into 1-dimention nano Li
2MnSiO
4/ C positive electrode powder.
Said organics additive is at least a in polyvinyl alcohol (PVA) and the ascorbic acid (VC).
Said organics additive is polyvinyl alcohol (PVA), is 10%～30% ratio and hydro-thermal raw materials mix with mass fraction.
Said organics additive is ascorbic acid (VC), is 3%～8% ratio and hydro-thermal raw materials mix with mass fraction.
Said hydrothermal system solution capacity accounts for the 60vol%～90vol% of retort volume.
Beneficial effect of the present invention is, adopts cheap organic additive as the pattern directed agents, through a kind of simple soft template method, prepares 1-dimention nano Li through regulating the hydro-thermal technological parameter
2MnSiO
4The positive electrode powder; Original position is introduced carbon source simultaneously, generates Li through further calcine technology original position
2MnSiO
4/ C composite positive pole has improved the electrode electro Chemical performance.With respect to solid phase method, sol-gal process, the pure phase that more is easy to get, the battery charging and discharging performance of electrode also obtains bigger raising.This synthetic method provides the method for preparing manganese silicate of lithium 1-dimention nano positive electrode, is with a wide range of applications in the anode material for lithium-ion batteries field.
Description of drawings
Fig. 1 is the SEM figure of positive electrode among the embodiment 1.
Fig. 2 is the SEM figure of positive electrode among the embodiment 2.
Fig. 3 is the SEM figure of positive electrode among the embodiment 3.
Fig. 4 is the SEM figure of positive electrode among the embodiment 4.
Fig. 5 is the SEM figure of positive electrode among the embodiment 5.
Fig. 6 is the SEM figure of positive electrode among the embodiment 6.
Fig. 7 is the SEM figure of positive electrode among the embodiment 7.
Fig. 8 is the SEM figure of positive electrode among the embodiment 8.
Embodiment
The present invention provides a kind of hydrothermal synthesis method for preparing nano wire/bar-shaped anode material for lithium ion battery manganese silicate of lithium.Below by embodiment, outstanding feature of the present invention and distinguishing feature are further elaborated, only be the present invention is described and never limit the present invention.
Embodiment 1
Take by weighing 0.12 mole of Lithium hydroxide monohydrate, each 0.015 mole of four water manganese acetates and tetraethoxysilane, LiOHH
2O: Mn (Ac)
24H
2O: tetraethoxysilane=8: 1: 1, put into ball grinder, add 10wt%PVA and deionized water, with 150 rev/mins speed ball millings 10 minutes; Then mixing material is poured in the stainless steel cauldron that has polytetrafluoroethyllining lining (volume 100ml), replenished deionized water, form the capacity of 80ml (accounting for 80vol%) liquid.Homogeneous reactor is put in sealing, with 10 rev/mins rotating speed, and 200 ℃ of crystallization 72h.Take out agitated reactor after reaction finishes, be cooled to room temperature.With alcohol and deionized water wash, filter, drying obtains the hydrothermal crystallizing product; Under high pure nitrogen atmosphere, 550 ℃ of calcining 8h promptly obtain Li
2MnSiO
4Powder.Discharge capacity reaches 229mAh/g first, and circulation volume is not less than 80% of capacity first for 59 times.
Embodiment 2
Take by weighing 0.03 mole of Lithium hydroxide monohydrate, each 0.015 mole of four water manganese acetates and tetraethoxysilane, LiOHH
2O: Mn (Ac)
24H
2O: tetraethoxysilane=2: 1: 1, put into ball grinder, add 20wt%PVA and deionized water, with 160 rev/mins speed ball millings 10 minutes; Then mixed solution is poured in the stainless steel cauldron that has polytetrafluoroethyllining lining (volume 100ml), replenished deionized water, form the capacity of 70ml (accounting for 70vol%) liquid.Homogeneous reactor is put in sealing, with 20 rev/mins rotating speed, at 180 ℃ of crystallization 48h.Take out agitated reactor after reaction finishes, be cooled to room temperature.With alcohol and deionized water wash, filter, drying obtains the hydrothermal crystallizing product; Under high-purity argon gas atmosphere, 650 ℃ of calcining 10h promptly obtain Li
2MnSiO
4Powder.Discharge capacity reaches 243mAh/g first, and circulation volume is not less than 80% of capacity first for 70 times.
Embodiment 3
Take by weighing 0.09 mole of Lithium hydroxide monohydrate, each 0.015 mole of four water manganese acetates and tetraethoxysilane, LiOHH
2O: Mn (Ac)
24H
2O: tetraethoxysilane=6: 1: 1, put into ball grinder, add 15wt%PVA and deionized water, with 170 rev/mins speed ball millings 10 minutes; Then mixed solution is poured in the stainless steel cauldron that has polytetrafluoroethyllining lining (volume 100ml), replenished deionized water, form the capacity of 60ml (accounting for 60vol%) liquid.Homogeneous reactor is put in sealing, with 30 rev/mins rotating speed, at 220 ℃ of crystallization 24h.Take out agitated reactor after reaction finishes, be cooled to room temperature.With alcohol and deionized water wash, filter, drying obtains the hydrothermal crystallizing product; Under high-purity argon gas atmosphere, 750 ℃ of calcining 5h promptly obtain Li
2MnSiO
4Powder.Discharge capacity reaches 236mAh/g first, and circulation volume is not less than 80% of capacity first for 50 times.
Embodiment 4
Take by weighing 0.06 mole of Lithium hydroxide monohydrate, each 0.015 mole of four water manganese acetates and tetraethoxysilane, LiOHH
2O: Mn (Ac)
24H
2O: tetraethoxysilane=4: 1: 1, put into ball grinder, add 30wt%PVA and deionized water, with 180 rev/mins speed ball millings 10 minutes; Then mixed solution is poured in the stainless steel cauldron that has polytetrafluoroethyllining lining (volume 100ml), replenished deionized water, form the capacity of 90ml (accounting for 90vol%) liquid.Homogeneous reactor is put in sealing, with 15 rev/mins rotating speed, at 150 ℃ of crystallization 60h.Take out agitated reactor after reaction finishes, be cooled to room temperature.With alcohol and deionized water wash, filter, drying obtains the hydrothermal crystallizing product; Under high pure nitrogen atmosphere, 800 ℃ of calcining 9h promptly obtain Li
2MnSiO
4Powder.Discharge capacity reaches 256mAh/g first, and circulation volume is not less than 80% of capacity first for 60 times.
Embodiment 5
Take by weighing 0.105 mole of Lithium hydroxide monohydrate, each 0.015 mole of four water manganese acetates and tetraethoxysilane, LiOHH
2O: Mn (Ac)
24H
2O: tetraethoxysilane=7: 1: 1, put into ball grinder, add 25wt%PVA and deionized water, with 190 rev/mins speed ball millings 10 minutes; Then mixed solution is poured in the stainless steel cauldron that has polytetrafluoroethyllining lining (volume 100ml), replenished deionized water, form the capacity of 85ml (accounting for 85vol%) liquid.Homogeneous reactor is put in sealing, with 25 rev/mins rotating speed, at 175 ℃ of crystallization 40h.Take out agitated reactor after reaction finishes, be cooled to room temperature.With alcohol and deionized water wash, filter, drying obtains the hydrothermal crystallizing product; Under high pure nitrogen atmosphere, 500 ℃ of calcining 7h promptly obtain Li
2MnSiO
4Powder.Discharge capacity reaches 217mAh/g first, and circulation volume is not less than 80% of capacity first for 45 times.
Embodiment 6
Take by weighing 0.06 mole of Lithium hydroxide monohydrate, each 0.015 mole of four water manganese acetates and tetraethoxysilane, LiOHH
2O: Mn (Ac)
24H
2O: tetraethoxysilane=4: 1: 1, put into ball grinder, add 3wt%VC and deionized water, with 150 rev/mins speed ball millings 10 minutes; Then mixed solution is poured in the stainless steel cauldron that has polytetrafluoroethyllining lining (volume 100ml), replenished deionized water, form the capacity of 80ml (accounting for 80vol%) liquid.Homogeneous reactor is put in sealing, with 10 rev/mins rotating speed, at 220 ℃ of crystallization 72h.Take out agitated reactor after reaction finishes, be cooled to room temperature.With alcohol and deionized water wash, filter, drying obtains the hydrothermal crystallizing product; Under high pure nitrogen atmosphere, 700 ℃ of calcining 10h promptly obtain Li
2MnSiO
4Powder.Discharge capacity reaches 257mAh/g first, and circulation volume is not less than 80% of capacity first for 55 times.
Embodiment 7
Take by weighing 0.12 mole of Lithium hydroxide monohydrate, each 0.015 mole of four water manganese acetates and tetraethoxysilane, LiOHH
2O: Mn (Ac)
24H
2O: tetraethoxysilane=8: 1: 1, put into ball grinder, add 5wt%VC and deionized water, with 200 rev/mins speed ball millings 10 minutes; Then mixed solution is poured in the stainless steel cauldron that has polytetrafluoroethyllining lining (volume 100ml), replenished deionized water, form the capacity of 90ml (accounting for 90vol%) liquid.Homogeneous reactor is put in sealing, with 20 rev/mins rotating speed, at 150 ℃ of crystallization 48h.Take out agitated reactor after reaction finishes, be cooled to room temperature.With alcohol and deionized water wash, filter, drying obtains the hydrothermal crystallizing product; Under high pure nitrogen atmosphere, 600 ℃ of calcining 5h promptly obtain Li
2MnSiO
4Powder.Discharge capacity reaches 233mAh/g first, and circulation volume is not less than 80% of capacity first for 70 times.
Embodiment 8
Take by weighing 0.03 mole of Lithium hydroxide monohydrate, each 0.015 mole of four water manganese acetates and tetraethoxysilane, LiOHH
2O: Mn (Ac)
24H
2O: tetraethoxysilane=2: 1: 1, put into ball grinder, add 8wt%VC and deionized water, with 170 rev/mins speed ball millings 10 minutes; Then mixed solution is poured in the stainless steel cauldron that has polytetrafluoroethyllining lining (volume 100ml), replenished deionized water, form the capacity of 60ml (accounting for 60vol%) liquid.Homogeneous reactor is put in sealing, with 30 rev/mins rotating speed, at 180 ℃ of crystallization 24h.Take out agitated reactor after reaction finishes, be cooled to room temperature.With alcohol and deionized water wash, filter, drying obtains the hydrothermal crystallizing product; Under high pure nitrogen atmosphere, 500 ℃ of calcining 10h promptly obtain Li
2MnSiO
4Powder.Discharge capacity reaches 243mAh/g first, and circulation volume is not less than 80% of capacity first for 67 times.
Claims (5)
1. the method for the auxiliary hydrothermal synthesis of one-dimensional nano pattern manganese silicate of lithium positive electrode of an organics additive; It is characterized in that; In raw material, add organic substance polyvinyl alcohol (PVA), ascorbic acid (VC); Prepare the hydrothermal synthesis method of nano wire/bar-shaped pattern manganese silicate of lithium as directed agents, its concrete steps are:
With Lithium hydroxide monohydrate, four water manganese acetates, tetraethoxysilane is parent stock according to x: 1: 1 (2≤x≤8) mole proportioning takes by weighing and is dissolved in the deionized water of certain volume amount; Be placed in the ball grinder; The organics additive that adds the certain mass mark; With 150～200 rev/mins rotating speed ball millings 10 minutes; Pour into and have in the teflon-lined stainless steel cauldron, after the sealing agitated reactor is put into rotatable homogeneous reactor with 10～30 rev/mins rotating speed, at 150 ℃～220 ℃ following hydro-thermal reaction 24～72h.Take out agitated reactor after reaction is accomplished, be cooled to room temperature, take out product.Wash, filter, after the drying, promptly obtain Li with deionized water and alcohol
2MnSiO
41-dimention nano positive electrode powder, further under high pure nitrogen, argon gas atmosphere, the calcination processing 5～10h through 500～800 ℃ obtains into 1-dimention nano Li
2MnSiO
4/ C positive electrode powder.
2. according to the method for the auxiliary hydrothermal synthesis of one-dimensional nano pattern manganese silicate of lithium positive electrode of the said organic additive of claim 1, it is characterized in that said organics additive is a kind of in polyvinyl alcohol (PVA) and the ascorbic acid (VC).
3. according to the method for the auxiliary hydrothermal synthesis of one-dimensional nano pattern manganese silicate of lithium positive electrode of the said organic additive of claim 1, it is characterized in that said organics additive polyvinyl alcohol (PVA) is 10%～30% ratio and hydro-thermal raw materials mix with mass fraction.
4. according to the method for the auxiliary hydrothermal synthesis of one-dimensional nano pattern manganese silicate of lithium positive electrode of the said organic additive of claim 1, it is characterized in that said organics additive is ascorbic acid (VC), is 3%～8% ratio and hydro-thermal raw materials mix with mass fraction.
5. according to the method for the auxiliary hydrothermal synthesis of one-dimensional nano pattern manganese silicate of lithium positive electrode of the said organic additive of claim 1, it is characterized in that said hydrothermal system solution capacity accounts for the 60vol%～90vol% of retort volume.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668605A (en) * | 2016-01-09 | 2016-06-15 | 青岛科技大学 | Preparation method of nest-like mesoporous cerium oxide with high specific surface area |
| CN107195864A (en) * | 2017-06-05 | 2017-09-22 | 齐鲁工业大学 | A kind of lithium ion battery Li2MnSiO4The preparation method of/C meso-porous nano composite positive poles |
| CN108649214A (en) * | 2018-05-07 | 2018-10-12 | 东北大学 | A kind of Mn2O3One-dimensional nano line and its preparation method and application |
| CN110061235A (en) * | 2019-03-29 | 2019-07-26 | 桂林理工大学 | The method of the tertiary cathode material of excellent chemical property is prepared by the structure regulating of soft template |
| CN110429266A (en) * | 2019-08-14 | 2019-11-08 | 咸阳师范学院 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN112264057A (en) * | 2020-10-09 | 2021-01-26 | 南北兄弟药业投资有限公司 | Nano fluorination catalyst for preparing R152a and preparation method thereof |
| CN112264035A (en) * | 2020-10-09 | 2021-01-26 | 南北兄弟药业投资有限公司 | Catalyst for preparing vinyl fluoride by gas phase removing hydrogen fluoride from 1, 1-difluoroethane |
| CN114566638A (en) * | 2022-03-02 | 2022-05-31 | 厦门大学 | Silicon nanowire, preparation method and application thereof, and preparation method of lithium ion battery cathode |
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2012
- 2012-04-12 CN CN201210113571.7A patent/CN102694173B/en not_active Expired - Fee Related
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|---|---|---|---|---|
| CN105668605A (en) * | 2016-01-09 | 2016-06-15 | 青岛科技大学 | Preparation method of nest-like mesoporous cerium oxide with high specific surface area |
| CN107195864A (en) * | 2017-06-05 | 2017-09-22 | 齐鲁工业大学 | A kind of lithium ion battery Li2MnSiO4The preparation method of/C meso-porous nano composite positive poles |
| CN107195864B (en) * | 2017-06-05 | 2019-09-24 | 齐鲁工业大学 | A kind of lithium ion battery Li2MnSiO4The preparation method of/C meso-porous nano composite positive pole |
| CN108649214A (en) * | 2018-05-07 | 2018-10-12 | 东北大学 | A kind of Mn2O3One-dimensional nano line and its preparation method and application |
| CN110061235A (en) * | 2019-03-29 | 2019-07-26 | 桂林理工大学 | The method of the tertiary cathode material of excellent chemical property is prepared by the structure regulating of soft template |
| CN110429266A (en) * | 2019-08-14 | 2019-11-08 | 咸阳师范学院 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN112264057A (en) * | 2020-10-09 | 2021-01-26 | 南北兄弟药业投资有限公司 | Nano fluorination catalyst for preparing R152a and preparation method thereof |
| CN112264035A (en) * | 2020-10-09 | 2021-01-26 | 南北兄弟药业投资有限公司 | Catalyst for preparing vinyl fluoride by gas phase removing hydrogen fluoride from 1, 1-difluoroethane |
| CN114566638A (en) * | 2022-03-02 | 2022-05-31 | 厦门大学 | Silicon nanowire, preparation method and application thereof, and preparation method of lithium ion battery cathode |
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