CN106711409A - Preparation method of tin-dioxide-supported carbon nanorod material - Google Patents
Preparation method of tin-dioxide-supported carbon nanorod material Download PDFInfo
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a tin-dioxide-supported carbon nanorod material. The method comprises the following steps: by using a cellulose raw material as the substrate, treating cellulose by an acid catalysis process to remove amorphous regions and impurity components in the cellulose, extracting a cellulose nanocrystal suspension, carrying out chemical supporting on the cellulose nanocrystals by using tin chloride to prepare tin-containing cellulose nanocrystals, and carrying out high-temperature oxidation-carbonization treatment to prepare the high-length-diameter-ratio tin-dioxide-supported carbon nanorod material of which the diameter is 10-30nm and the length is 150-350nm. By effectively utilizing the biomass material cellulose, the method has the characteristics of wide raw material sources, renewable raw material and no pollution. The carbon nanorods have the advantage of excellent electric conductivity and have the size which is not possessed by the past carbon material, and have favorable effects of relieving the volume change and improving the cycle performance of batteries.
Description
Technical field
The invention belongs to field of lithium ion battery cathode material preparation, especially with regard to a kind of tin ash load type carbon nanometer rods
The method of material.
Background technology
With the development of society, environmental pollution and the challenge of energy crisis are increasingly serious, and green energy resource turns into countries in the world
Research and development focus.Lithium ion battery with light weight, pollutes small, operating voltage as a kind of rechargable power supplies of Novel clean
High, energy resource density is big, the advantages of have extended cycle life, wide application prospect, quilt are illustrated in national defence, electric motor car and electronic applications
It is described as the ideal source of 21 century.
In lithium ion battery, negative material is one of key factor of influence battery capacity service life.Current business
Product lithium ion battery mainly uses graphite or modified graphite as negative material, with good cycle performance and forthright again
Can, but its theoretical specific capacity is only 372 mAh/g, it is difficult to makes extensively in the field of the high-energy-densities such as electric automobile requirement
With.In order to improve the specific capacity of battery, the graphite alternative materials that high power capacity can be kept under low potential need to be found.In recent years,
Silicon alloy, tin alloy and SnO2、TiO2、Fe2O3、Co3O4、MnO2、MoO3Turn into research heat both domestic and external Deng metal oxide
Point.Wherein, the specific capacity of tin ash negative material is high（Theoretical specific capacity is 782 mAh）, embedding lithium potential is low, energy density
It is high, have a safety feature, aboundresources, low cost and other advantages, with very big application potential.But titanium dioxide lithium is in charge and discharge process
It is middle there is serious bulk effect, circulation during the repeatedly embedded and abjection of lithium ion easily cause efflorescence and agglomeration, lead
Irreversible capacity is big first, cyclical stability is poor to cause material, and repeatedly after circulation, electrode is gradually destroyed.It is how effective
Alleviate bulk effect and powder phenomenon-tion, the cyclical stability for improving electrode has become current research tin ash negative material
It is crucial.Current researcher is mainly solved the above problems by preparing nanostructured tin dioxide and structure composite.
The A of CN 104868109 disclose the side that a kind of porous carbon load tin ash prepares lithium ion battery negative material
Method.The high dispersive compound of the method signal bronze first and carbon, then copper is selectively removed with nitric acid, tin is oxidized into dioxy
Change tin and be stored in porous carbon duct in nanosizing form, remained above after 50 weeks when having obtained current density for 100 mA/g
High-capacity cathode material of the stabilization higher than 300 mAh/g when 900 mAh/g, current density are 1 A/g.Wang Wenfeng（Wang Wen peaks
(2015) application Shanghai University Master's thesis of the tin ash-C-base composte material in lithium ion battery）, Jiang Yinzhu
Deng（Jiang Yinzhu, Xu Yue, the preparation of tight (2011) tin ash-graphene nano composite lithium ion battery cathode
Made a summary with the Chinese material Conference Papers of performance characterization 2011 and collected）Tin ash is carried on graphene oxide by different way
On, it is 891.7 mAh/g, the cathode of lithium battery of 719 mAh/g that cycle charging capacity is prepared for respectively.Similar, high length-diameter ratio
Nano-carbon material such as CNT, carbon nano-fiber etc. are also used for loading tin ash.Ding etc. reports a kind of sandwich knot
Carbon nano tube/tin dioxide/the carbon composite of structure, tin ash content reaches 80% (mass fraction), by 60 charge and discharges
After electricity circulation, reversible capacity is still up to 505 mAh/g（Ding S, Chen J S, Lou X W. CNTs@SnO2@Carbon
Coaxial Nanocables with High Mass Fraction of SnO 2, for Improved Lithium
Storage[J]. Chemistry-An Asian Journal, 2011, 6(9):2278–2281）.
Tin ash has larger application potential as the negative material of lithium ion battery, by the structure for optimizing material
And composition, particularly Nanostructure fabrication tin ash and with carbon material or other materials such as amorphous carbon, CNT, Graphene
Material is compound, not only contributes to increase the area and reaction site at electrode/electrolyte interface, improves electrode capacity, and can have
The internal stress that effect buffer volumes change causes, reduces irreversible capacity decay, improves cycle performance, and this will be following high-performance lithium
The development and commercialization of ion battery lay the foundation.But, the storage lithium process of tin ash is being embedded in repeatedly by lithium ion
With take off realization, the characteristics of based on the process and mechanism, the Volume Changes and irreversible capacity loss of stannic oxide electrode
It is difficult to avoid completely.Although in the past research in about tin ash negative material nanosizing and its with various carbon-based or other materials
The existing numerous studies report of the Composite of material, and have certain effect, but two to alleviating Volume Changes, improving cycle performance
The tin oxide problem that irreversible capacity is big first, cyclical stability is poorer than carbon material does not have basic solution, and this is also big at present
The common problem that part non-carbons negative material is faced.In order to reduce the solution of this problem as far as possible, it is necessary to carbon-based load
Body carries out the size Control that becomes more meticulous, and then causes that the Volume Changes of electrode are integrally controllable, while ensureing the steady of carrier conductivity energy
Qualitative, the work of this respect need researcher further research and exploration.
The content of the invention
It is an object of the invention to provide a kind of method of tin ash load type carbon nano-bar material, the present invention effectively profit
With biological material cellulose, with raw material sources are wide, renewable, pollution-free feature, while the carbon nano rod have it is superior
Electric conductivity and conventional carbon material not available for size advantage, can alleviate Volume Changes, improve battery cycle performance have
Good effect.
To reach above-mentioned purpose, the technical scheme is that：A kind of side of tin ash load type carbon nano-bar material
Method, comprises the following steps：Using cellulosic raw material as base material, cellulose is processed with acid catalyzed process, remove fiber
Amorphous region and impurity component in element, extract Cellulose nanocrystal suspension, with stannic chloride to Cellulose nanocrystal
Learn load and prepare stanniferous Cellulose nanocrystal, it is long then by after high-temperature oxydation-charing process, preparing a diameter of 10-30 nm
It is 150-350 nm to spend, with the tin ash load type carbon nano-bar material compared with big L/D ratio.
The extracting method of described Cellulose nanocrystal suspension is：Cellulose is placed in fibre is configured as in hydrochloric acid solution
The suspension of element is tieed up, suspension is transferred to water heating kettle and is reacted, after reaction terminates, reaction solution stratification removed
Layer clear liquid obtains Cellulose nanocrystal suspension；Wherein, described concentration of hydrochloric acid solution is 5 mol/L；Cellulose is in hydrochloric acid
Solid content be 0.005-0.05 g/mL；The reaction temperature that suspension liquid is tied up in water heating kettle is 100-120 DEG C, during reaction
Between be 1-5h.
Described cellulosic raw material is using the one kind in cellulose crystallite, cotton, paper scrap, wood chip, bacteria cellulose.
Described carries out the operation side that chemical load prepares stanniferous Cellulose nanocrystal to Cellulose nanocrystal with stannic chloride
Method is：Add ethanol and deionized water in the Cellulose nanocrystal suspension that will be prepared, wherein suspension/ethanol/go from
The volume ratio of sub- water（v/v）=1：（1~3）：（1~2）, 35 ~ 45 DEG C are cooled to, add the stannic chloride of 10 ~ 20 wt%, stirring and dissolving
After instill appropriate ammoniacal liquor and adjust PH to neutrality, after reaction continues 2 h, reactant is collected by centrifugation, washed with deionized water and alcohol
Wash, stanniferous Cellulose nanocrystal is obtained after being vacuum dried through 80 DEG C.
Described stanniferous Cellulose nanocrystal is oxidized-and charing is the step of prepare tin ash load carbon nano rod：Will
The stanniferous Cellulose nanocrystal for preparing is placed in CVD tube furnaces under air atmosphere, high temperature oxidation process is carried out first, then
Protective gas is passed through, the carbon nano rod of tin ash load is prepared at high temperature；Wherein described high temperature oxidation process
When temperature be 200-350 DEG C, by 1-3 h high-temperature process；Described protective gas uses nitrogen or argon gas；It is described
Protective gas be passed through after using being progressively warming up to 1000-1500 DEG C, it is bar-shaped by obtaining being shaped as after 1-3h charings
A diameter of 10-30 nm, length is the tin ash load type carbon nano-bar material of 150-350 nm.
The beneficial effects of the invention are as follows：A kind of side of tin ash load type carbon nano-bar material proposed by the invention
Method, is effectively utilized biological material cellulose, with raw material sources are wide, renewable, pollution-free feature；By regulating and controlling cellulose
Raw material, acid concentration, hydrolysis temperature, hydrolysis time factor in nanocrystalline preparation process, realize Cellulose nanocrystal and final
The Modulatory character of carbon nano rod size；The tin ash load type carbon nano-bar material has body in lithium ion battery negative field
The characteristics of product changes overall controllable, carrier conductivity stabilizability is good, with the institute such as traditional carbon fibres, Graphene, CNT
The size advantage not possessed.
Specific embodiment
Embodiment 1
A kind of method of tin ash load type carbon nano-bar material of the present embodiment, comprises the following steps：First by commercialization
Microcrystalline cellulose（Production code member 68005761, traditional Chinese medicines reagent）Fully infiltrated in the hydrochloric acid solution that concentration is 5 mol/L, turned
Move on in water heating kettle, the solid content of microcrystalline cellulose remains 0.008 g/mL.Reaction carries out 5 h, question response at 100 DEG C
After kettle natural cooling, diluted with deionized water；Supernatant liquor is removed after stratification, it is repeated multiple times until dispersion liquid is formed
The suspension of stabilization.Then it is configured to mixed solution to addition ethanol and deionized water in suspension（Suspension/ethanol/go from
Sub- water（v/v）=1:2:2）, 35 DEG C are cooled to, the stannic chloride of 10 wt% is added, appropriate ammoniacal liquor regulation PH is instilled after stirring and dissolving
To neutral, after reaction continues 2 h, reactant is collected by centrifugation, with deionized water and ethanol wash, after 80 DEG C of vacuum drying
Obtain stanniferous Cellulose nanocrystal.
Then stanniferous Cellulose nanocrystal is placed in CVD tube furnaces under air atmosphere, is carried out at 200 DEG C of oxidations of high temperature
Reason, then passes to protective gas nitrogen, is progressively warming up to 1000 DEG C, by obtaining tin ash load type carbon after 3 h charings
Nano-bar material.
Tested through field emission scanning electron microscope, tin ash load type carbon nano-bar material average diameter manufactured in the present embodiment
It is 30 nm, average length is 350 nm.
A kind of method of tin ash load type carbon nano-bar material that the present embodiment is proposed, is effectively utilized biomass
Material fiber element, with raw material sources it is wide, renewable, it is pollution-free the features such as；In by regulating and controlling Cellulose nanocrystal preparation process
The factors such as raw material, acid concentration, hydrolysis temperature, hydrolysis time, realize Cellulose nanocrystal and final carbon nano rod size
Modulatory character；The tin ash load type carbon nano-bar material in lithium ion battery negative field there are Volume Changes integrally may be used
Control, the characteristics of carrier conductivity stabilizability is good, with the size that traditional carbon fibres, Graphene, CNT etc. are not available
Advantage.
Embodiment 2
A kind of method of tin ash load type carbon nano-bar material of the present embodiment, comprises the following steps：First by commercialization
Microcrystalline cellulose（Production code member 68005761, traditional Chinese medicines reagent）Fully infiltrated in the hydrochloric acid solution that concentration is 5 mol/L, turned
Move on in water heating kettle, the solid content of microcrystalline cellulose remains 0.05 g/mL.Reaction carries out 2 h, question response kettle at 100 DEG C
After natural cooling, diluted with deionized water；Supernatant liquor is removed after stratification, it is repeated multiple times until dispersion liquid is formed surely
Fixed suspension.Then it is configured to mixed solution to addition ethanol and deionized water in suspension（Suspension/ethanol/deionization
Water（v/v）=1:3:2）, be cooled to 45 DEG C, add the stannic chloride of 20 wt%, instilled after stirring and dissolving appropriate ammoniacal liquor adjust PH to
Neutrality, after reaction continues 2 h, reactant is collected by centrifugation, and with deionized water and ethanol wash, is obtained after being vacuum dried through 80 DEG C
To stanniferous Cellulose nanocrystal.
Then stanniferous Cellulose nanocrystal is placed in CVD tube furnaces under air atmosphere, is carried out at 350 DEG C of oxidations of high temperature
Reason, then passes to protective gas argon gas, is progressively warming up to 1500 DEG C, by obtaining tin ash load type carbon after 1 h charings
Nano-bar material.
Tested through field emission scanning electron microscope, tin ash load type carbon nano-bar material average diameter manufactured in the present embodiment
It is 10 nm, average length is 150 nm.
A kind of method of tin ash load type carbon nano-bar material that the present embodiment is proposed, is effectively utilized biomass
Material fiber element, with raw material sources are wide, renewable, pollution-free feature；By regulating and controlling Cellulose nanocrystal preparation process Central Plains
Material, acid concentration, hydrolysis temperature, hydrolysis time factor, realize the adjustable of Cellulose nanocrystal and final carbon nano rod size
Control property；The tin ash load type carbon nano-bar material has Volume Changes integrally controllable in lithium ion battery negative field, carries
The characteristics of body electric conductivity good stability, with the size advantage that traditional carbon fibres, Graphene, CNT etc. are not available.
Embodiment 3
A kind of method of tin ash load type carbon nano-bar material of the present embodiment, comprises the following steps：First by commercialization
Microcrystalline cellulose（Production code member 68005761, traditional Chinese medicines reagent）Fully infiltrated in the hydrochloric acid solution that concentration is 5 mol/L, turned
Move on in water heating kettle, the solid content of microcrystalline cellulose remains 0.02 g/mL.Reaction carries out 4 h, question response kettle at 110 DEG C
After natural cooling, diluted with deionized water；Supernatant liquor is removed after stratification, it is repeated multiple times until dispersion liquid is formed surely
Fixed suspension.Then it is configured to mixed solution to addition ethanol and deionized water in suspension（Suspension/ethanol/deionization
Water（v/v）=1:2:1）, be cooled to 35 DEG C, add the stannic chloride of 20 wt%, instilled after stirring and dissolving appropriate ammoniacal liquor adjust PH to
Neutrality, after reaction continues 2 h, reactant is collected by centrifugation, and with deionized water and ethanol wash, is obtained after being vacuum dried through 80 DEG C
To stanniferous Cellulose nanocrystal.
Then stanniferous Cellulose nanocrystal is placed in CVD tube furnaces under air atmosphere, is carried out at 250 DEG C of oxidations of high temperature
Reason, then passes to protective gas nitrogen, is progressively warming up to 1200 DEG C, by obtaining tin ash load type carbon after 3h charings
Nano-bar material.
Tested through field emission scanning electron microscope, tin ash load type carbon nano-bar material average diameter manufactured in the present embodiment
It is 20 nm, average length is 216 nm.
A kind of method of tin ash load type carbon nano-bar material that the present embodiment is proposed, is effectively utilized biomass
Material fiber element, with raw material sources are wide, renewable, pollution-free feature；By regulating and controlling Cellulose nanocrystal preparation process Central Plains
Material, acid concentration, hydrolysis temperature, hydrolysis time factor, realize the adjustable of Cellulose nanocrystal and final carbon nano rod size
Control property；The tin ash load type carbon nano-bar material has Volume Changes integrally controllable in lithium ion battery negative field, carries
The characteristics of body electric conductivity good stability, with the size advantage that traditional carbon fibres, Graphene, CNT etc. are not available.
Embodiment 4
A kind of method of tin ash load type carbon nano-bar material of the present embodiment, comprises the following steps：First by commercialization
Bacteria cellulose（The moral Food Co., Ltd of Hainan hundred million, food-grade）Fully infiltrated in the hydrochloric acid solution that concentration is 5 mol/L,
It is transferred in water heating kettle, the solid content of microcrystalline cellulose remains 0.005 g/mL.Reaction carries out 1 h, question response at 120 DEG C
After kettle natural cooling, diluted with deionized water；Supernatant liquor is removed after stratification, it is repeated multiple times until dispersion liquid is formed
The suspension of stabilization.Then it is configured to mixed solution to addition ethanol and deionized water in suspension（Suspension/ethanol/go from
Sub- water（v/v）=1:1.5:1）, 40 DEG C are cooled to, the stannic chloride of 20 wt% is added, appropriate ammoniacal liquor regulation is instilled after stirring and dissolving
PH after reaction continues 2 h, reactant is collected by centrifugation to neutrality, with deionized water and ethanol wash, through 80 DEG C of vacuum drying
After obtain stanniferous Cellulose nanocrystal.
Then stanniferous Cellulose nanocrystal is placed in CVD tube furnaces under air atmosphere, is carried out at 260 DEG C of oxidations of high temperature
Reason, then passes to protective gas argon gas, is progressively warming up to 1180 DEG C, by obtaining tin ash load type carbon after 2 h charings
Nano-bar material.
Tested through field emission scanning electron microscope, tin ash load type carbon nano-bar material average diameter manufactured in the present embodiment
It is 15 nm, average length is 250 nm.
A kind of method of tin ash load type carbon nano-bar material that the present embodiment is proposed, is effectively utilized biomass
Material fiber element, with raw material sources are wide, renewable, pollution-free feature；By regulating and controlling Cellulose nanocrystal preparation process Central Plains
Material, acid concentration, hydrolysis temperature, hydrolysis time factor, realize the adjustable of Cellulose nanocrystal and final carbon nano rod size
Control property；The tin ash load type carbon nano-bar material has Volume Changes integrally controllable in lithium ion battery negative field, carries
The characteristics of body electric conductivity good stability, with the size advantage that traditional carbon fibres, Graphene, CNT etc. are not available.
Embodiment 5
A kind of method of tin ash load type carbon nano-bar material of the present embodiment, comprises the following steps：First by commercialization
Bacteria cellulose（The moral Food Co., Ltd of Hainan hundred million, food-grade）Fully infiltrated in the hydrochloric acid solution that concentration is 5 mol/L,
It is transferred in water heating kettle, the solid content of microcrystalline cellulose remains 0.01 g/mL.Reaction carries out 3 h, question response at 105 DEG C
After kettle natural cooling, diluted with deionized water；Supernatant liquor is removed after stratification, it is repeated multiple times until dispersion liquid is formed
The suspension of stabilization.Then it is configured to mixed solution to addition ethanol and deionized water in suspension（Suspension/ethanol/go from
Sub- water（v/v）=1:1:2）, 38 DEG C are cooled to, the stannic chloride of 18 wt% is added, appropriate ammoniacal liquor regulation PH is instilled after stirring and dissolving
To neutral, after reaction continues 2 h, reactant is collected by centrifugation, with deionized water and ethanol wash, after 80 DEG C of vacuum drying
Obtain stanniferous Cellulose nanocrystal.
Then stanniferous Cellulose nanocrystal is placed in CVD tube furnaces under air atmosphere, is carried out at 240 DEG C of oxidations of high temperature
Reason, then passes to protective gas argon gas, is progressively warming up to 1300 DEG C, by obtaining tin ash support type after 1.5 h charings
Carbon nano rod material.
Tested through field emission scanning electron microscope, tin ash load type carbon nano-bar material average diameter manufactured in the present embodiment
It is 26 nm, average length is 310 nm.
The method that the carbon nano rod that the present embodiment is proposed loads tin ash, is effectively utilized biological material fiber
Element, with raw material sources are wide, renewable, pollution-free feature；It is dense by regulating and controlling raw material in Cellulose nanocrystal preparation process, acid
Degree, hydrolysis temperature, hydrolysis time factor, realize the Modulatory character of Cellulose nanocrystal and final carbon nano rod size；Should
Tin ash load type carbon nano-bar material has Volume Changes integrally controllable in lithium ion battery negative field, carrier conductivity
The characteristics of stabilizability is good, with the size advantage that traditional carbon fibres, Graphene, CNT etc. are not available.
Claims (5)
1. a kind of method of tin ash load type carbon nano-bar material, it is characterised in that comprise the following steps：Using cellulose
Raw material are processed cellulose as base material with acid catalyzed process, remove the amorphous region in cellulose and impurity component, are carried
Extracting cellulose nanocrystal suspension, carries out chemical load and prepares stanniferous Cellulose nanocrystal with stannic chloride to Cellulose nanocrystal,
Then by after high-temperature oxydation-charing process, preparing a diameter of 10-30 nm, length is 150-350 nm, with relatively greatly enhancing
Footpath than tin ash load type carbon nano-bar material.
2. a kind of method of tin ash load type carbon nano-bar material as claimed in claim 1, it is characterised in that described
The extracting method of Cellulose nanocrystal suspension is：Cellulosic raw material is placed in hydrochloric acid solution and is configured as the outstanding of cellulose
Supernatant liquid, is transferred to suspension water heating kettle and is reacted, after reaction terminates, by reaction solution stratification, removes supernatant liquor and obtains
To Cellulose nanocrystal suspension；Wherein, described concentration of hydrochloric acid solution is 5 mol/L；Solid content of the cellulose in hydrochloric acid
It is 0.005-0.05 g/mL；It is 100-120 DEG C that suspension liquid ties up to reaction temperature in water heating kettle, the reaction time is 1-
5h。
3. a kind of method of tin ash load type carbon nano-bar material as claimed in claim 2, it is characterised in that described
Cellulosic raw material is using the one kind in cellulose crystallite, cotton, paper scrap, wood chip, bacteria cellulose.
4. a kind of method of tin ash load type carbon nano-bar material as claimed in claim 1, it is characterised in that described
Chemical load carried out to Cellulose nanocrystal with stannic chloride prepare the operating method of stanniferous Cellulose nanocrystal be：To prepare
Cellulose nanocrystal suspension in add ethanol and deionized water to be configured to mixed solution, wherein suspension/ethanol/deionization
The volume ratio of water（v/v）=1：（1~3）：（1~2）, after being cooled to 35-45 DEG C, the stannic chloride of 10 ~ 20 wt% is added, stir molten
Ammoniacal liquor is instilled after solution and adjusts PH to neutrality, after reaction continues 2 h, reactant is collected by centrifugation, with deionized water and ethanol wash,
Stanniferous Cellulose nanocrystal is obtained after being vacuum dried through 80 DEG C.
5. a kind of method of tin ash load type carbon nano-bar material as claimed in claim 1, it is characterised in that described
Stanniferous Cellulose nanocrystal is oxidized-and charing is the step of prepare tin ash load carbon nano rod：It is stanniferous by what is prepared
Cellulose nanocrystal is placed in CVD tube furnaces under air atmosphere, and high temperature oxidation process is carried out first, then passes to protectiveness gas
Body, prepares the carbon nano rod of tin ash load at high temperature；Temperature during wherein described high temperature oxidation process is
200-350 DEG C, by 1-3 h high-temperature process；Described protective gas uses nitrogen or argon gas；Described protectiveness gas
Body be passed through after using being progressively warming up to 1000-1500 DEG C, by obtaining being shaped as bar-shaped a diameter of 10 after 1-3h charings-
30 nm, length is the tin ash load type carbon nano-bar material of 150-350 nm.
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| CN109686945A (en) * | 2018-12-20 | 2019-04-26 | 电子科技大学 | A kind of method of low temperature self-activation preparation carbon coating Tin Composite Material |
| CN109841825A (en) * | 2019-03-29 | 2019-06-04 | 华南理工大学 | A kind of method that tin prepares lithium ion battery negative material in recycling electroplating sludge |
| CN110078177A (en) * | 2019-04-19 | 2019-08-02 | 广西民族大学 | A kind of SnO2- GAC particle and its preparation method and application |
| CN110136983A (en) * | 2019-05-13 | 2019-08-16 | 东南大学 | Nitrogen oxidation tin nano column array/poroid activated carbon fiber integrated material and preparation method thereof and electrochemical energy storage application |
| CN112018360A (en) * | 2020-08-26 | 2020-12-01 | 合肥国轩高科动力能源有限公司 | Lithium ion battery cathode material, preparation method thereof and lithium ion battery |
| CN112768655A (en) * | 2021-01-11 | 2021-05-07 | 上海应用技术大学 | Preparation method of tin dioxide @ oxidized bacterial cellulose/reduced graphene oxide electrode material |
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| CN109686945A (en) * | 2018-12-20 | 2019-04-26 | 电子科技大学 | A kind of method of low temperature self-activation preparation carbon coating Tin Composite Material |
| CN109686945B (en) * | 2018-12-20 | 2021-07-02 | 电子科技大学 | Method for preparing carbon-coated tin-based composite material through low-temperature self-activation |
| CN109841825A (en) * | 2019-03-29 | 2019-06-04 | 华南理工大学 | A kind of method that tin prepares lithium ion battery negative material in recycling electroplating sludge |
| CN109841825B (en) * | 2019-03-29 | 2021-10-26 | 华南理工大学 | Method for preparing lithium ion battery cathode material by recycling tin in electroplating sludge |
| CN110078177A (en) * | 2019-04-19 | 2019-08-02 | 广西民族大学 | A kind of SnO2- GAC particle and its preparation method and application |
| CN110136983A (en) * | 2019-05-13 | 2019-08-16 | 东南大学 | Nitrogen oxidation tin nano column array/poroid activated carbon fiber integrated material and preparation method thereof and electrochemical energy storage application |
| CN110136983B (en) * | 2019-05-13 | 2021-01-26 | 东南大学 | Tin oxynitride nanorod array/porous active carbon fiber integrated material and preparation method and electrochemical energy storage application thereof |
| CN112018360A (en) * | 2020-08-26 | 2020-12-01 | 合肥国轩高科动力能源有限公司 | Lithium ion battery cathode material, preparation method thereof and lithium ion battery |
| CN112018360B (en) * | 2020-08-26 | 2022-02-18 | 合肥国轩高科动力能源有限公司 | Lithium ion battery cathode material, preparation method thereof and lithium ion battery |
| CN112768655A (en) * | 2021-01-11 | 2021-05-07 | 上海应用技术大学 | Preparation method of tin dioxide @ oxidized bacterial cellulose/reduced graphene oxide electrode material |
| CN112768655B (en) * | 2021-01-11 | 2022-06-28 | 上海应用技术大学 | Preparation method of tin dioxide @ oxidized bacterial cellulose/reduced graphene oxide electrode material |
| CN115465883A (en) * | 2022-06-22 | 2022-12-13 | 万向一二三股份公司 | Preparation method of tin oxide/carbon fiber composite negative electrode material |
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