CN106229490A - A kind of preparation method and application of the stannum carbon composite nano granule of hollow structure - Google Patents
A kind of preparation method and application of the stannum carbon composite nano granule of hollow structure Download PDFInfo
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- CN106229490A CN106229490A CN201610815150.7A CN201610815150A CN106229490A CN 106229490 A CN106229490 A CN 106229490A CN 201610815150 A CN201610815150 A CN 201610815150A CN 106229490 A CN106229490 A CN 106229490A
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides the preparation method and application of the stannum carbon composite nano granule of a kind of hollow structure.The preparation method of the stannum carbon composite nano granule of hollow structure: start with from tin base cathode material, a kind of method attempting using new reversible structure metal-organic framework materials, the approach of hollow nanometer material is prepared in conjunction with template, by minimum nanometer tin particles coat in agraphitic carbon, it is prepared for hollow N doping stannum/carbon composite.Hollow stannum carbon granule diameter 400 600nm prepared by the present invention, wall thickness 150 200nm, granule smooth-shaped, good dispersion.The stannum carbon composite nano granule of hollow structure of invention research can improve the cycle performance of battery as negative material, provides new research method for tin-based material as the volumetric expansion problem of lithium ion battery negative material.
Description
Technical field
The invention provides the preparation method and application of the stannum carbon composite nano granule of a kind of hollow structure.
Technical background
Industrial energy is mainly fossil class A fuel A at present, but these raw materials are due to non-renewable and combustion product dirt
Metachromia so that it is using and in terms of development by a definite limitation.People need the regenerative resource developing environmental protection to replace passing
The fossil energy of system, such as wind energy, solar energy, tide energy etc..Although people have had very in the technology utilize regenerative resource
Big breakthrough, but they also have clearly disadvantageous.Either the production capacity of wind-powered electricity generation or solar electrical energy generation industry by season and
The impact of weather is very big, and due to less stable, is often only used for domestic life electricity consumption, is difficult to be incorporated to industrial electrical network
In.To utilize regenerative resource to provide lasting electric energy fully, will be to energy storage system, especially electrical energy storage system
Higher performance requirement is proposed.It is low that lithium ion battery has difficulty of processing, and safety coefficient is high, energy density and cycle performance simultaneously
The advantage such as reliable has obtained Preliminary Applications in terms of electrokinetic cell.Following lithium ion battery will be utilized the most widely,
There is considerable development prospect.
The theoretical capacity of stannum is higher, stores up lithium better performances.Although simple stannum makees to have during negative material 990mAh g-1
Above theoretical capacity, but it is faced with the material structure destruction that volumetric expansion causes, the problem that granule atomization is reunited.This change
Change can make active material peel off from collector, thus causes electrode " to inactivate ", and capacity reduces.Therefore it is changed
Property.
Hollow structure cavity has cushioning effect to volumetric expansion during Lithium-ion embeding/abjection, is possible to prevent lattice
Structural deterioration, improves cyclical stability, and hollow micro-nano structure also can reduce the diffusion length of lithium ion, improves leading of electrode
Power.The present invention starts with from tin base cathode material, attempts using the side of a kind of new reversible structure metal-organic framework materials
Method, prepares the approach of hollow nanometer material in conjunction with template, by minimum nanometer tin particles coat in agraphitic carbon, is prepared for
Hollow N doping stannum/carbon composite, is coated with by the nanorize of tin particles, carbon, constructs hollow structure and carry out etc. to solve stannum and filling
Volumetric expansion in discharge process and agglomeration traits.The method that the one pot of paddling process used prepares metal-organic framework materials is anti-
Answering condition to require relatively low, less energy intensive, productivity is higher, applies on tin ion, and the wall thickness control for hollow structure accurately has
Effect.It addition, p-phenylenediamine has carried out natural N doping to granule in monomer reaction so that it is electric conductivity improves.
Summary of the invention
The invention provides the preparation method of the stannum carbon composite nano granule of a kind of hollow structure, first prepare organic carbon
Ball template, is subsequently added into the solution of metallic tin ion to construct hollow structure.Treat powder collection after hollow structure molding, forge
Burn, finally give the stannum carbon composite nano granule with hollow structure.
Technical scheme is as follows:
The preparation method of the stannum carbon composite nano granule of hollow structure:
1) be 1:4～3:1 in mass ratio by catechol monomer dropping boronic acid monomer solution extremely in, be subsequently adding
The stannic chloride pentahydrate solution of 1.5mg～10mg/mL, at room temperature sustained response 5～10 hours；After reaction terminates, by product
Washing is dried, and obtains hollow metal-organic nanometer granule；
2) hollow metal-organic nanometer granule is placed in tube furnace, 500～1000 DEG C of calcinings 1～5 under argon shield
Hour, obtain hollow tin carbon nanometer granule.
Optimum condition is as follows:
Catechol monomer is 1:2～2:1 with the mass ratio of boronic acid monomer.
The stannum carbon composite nano granule of hollow structure prepared by the present invention is for lithium ion battery negative material, preparation
100mg·mL-1The N-Methyl pyrrolidone solution of polyvinylidene fluoride, by active material sample, carbon black, PVDF in mass ratio
Mix for 8:1:1, grind fully, mix homogeneously.Electrode slurry preamble obtained is uniformly coated on clean copper sheet, at 80 DEG C
Lower vacuum drying 24h.With clean copper foil-clad preamble gained dry paint copper sheet, compressing under the pressure of 10MPa, i.e. make
Obtain electrode slice sample.Electrode slice sample punching press is divided into the disk of diameter about 10mm.Electro-chemical test uses button cell system
(CR2032), with the stannum carbon composite nano granule of hollow structure as working electrode, using lithium metal as to electrode, barrier film uses
Celgard2400 lithium ion battery separator, electrolyte system is 1mol L-1LiPF6/ EC+DMC+EMC (volume ratio 1:1:
1).With 200mA g-1Electric current density carry out charge-discharge test.Test first charge-discharge capacity, hollow stannum under the same conditions
The capacity of discharge cycles first of carbon granule electrode has reached 1044mAh g-1, and after 250 circulations, still there is 480mAh g-1Capacity, although and nanometer tin mosaic electrode shows close to theoretical capacity (994mAh g in discharge cycles first-1)
Performance, but 100 circulation after be reduced to 90mAh g-1.The stannum carbon of the hollow structure of this explanation present invention research is multiple
Close nano-particle material and can improve the cycle performance of battery as negative material, bear as lithium ion battery for tradition tin-based material
The volumetric expansion problem of pole material provides a kind of new research method.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the stannum carbon composite nano particulate samples of embodiment 1 hollow structure.
Fig. 2 is the transmission electron microscope picture of the stannum carbon composite nano particulate samples of embodiment 2 hollow structure.
Fig. 3 is the scanning electron microscope (SEM) photograph of the stannum carbon composite nano particulate samples of embodiment 3 hollow structure.
Fig. 4 is that the EDS of the stannum carbon composite nano particulate samples of embodiment 5 hollow structure can spectrogram.
Fig. 5 is the scanning electron microscope (SEM) photograph of the stannum carbon composite nano particulate samples of embodiment 6 hollow structure.
Fig. 6 is the transmission electron microscope picture of the stannum carbon composite nano particulate samples of embodiment 6 hollow structure.
Fig. 7 is that the EDS of the stannum carbon composite nano particulate samples of embodiment 6 hollow structure can spectrogram.
Fig. 8 is that the stannum carbon composite nano particulate samples of embodiment 6 hollow structure is as 250 cyclic curves of negative material.
Detailed description of the invention
Raw material used in the embodiment of the present invention is commercial products, and purity is analytical pure.
The pattern of hollow structure stannum carbon composite nano granule prepared by the present invention is by scanning electron microscope (SEM) and saturating
Penetrate ultramicroscope (TEM) display.Electro-chemical test uses button cell system (CR2032), in being coated with blend polymer
Empty stannic oxide nanometer micro-sphere material is working electrode, uses lithium metal as to electrode, and barrier film uses Celgard 2400 lithium
Ion battery barrier film, electrolyte system is 1mol/L LiPF6/EC+DMC+EMC (volume ratio 1:1:1), with 200mA g-1Electricity
Stream carries out charge-discharge test.
Embodiment 1:
1) being dissolved in 10mL absolute methanol by 10mg catechol monomer, ultrasonic disperse is uniform；By molten for 20mg boronic acid monomer
Liquid is dissolved in 10mL absolute methanol, and ultrasonic disperse is uniform.Drop in the case of catechol monomer solution is stirred at room temperature
In boronic acid monomer solution, add the stannic chloride pentahydrate solution of 10mL 2mg/mL after dropping immediately, at room temperature continue anti-
Answer 8 hours.After reaction terminates, product absolute methanol is cleaned to remove undesired impurities, finally product is dried, in i.e. obtaining
Empty metallo-organic nanoparticle.
2) being placed in tube furnace by prepared hollow metal-organic nanometer granule, under argon shield, 500 DEG C of calcinings 1 are little
Time, obtain hollow tin carbon nanometer granule.
This example prepares thin wall hollow tin carbon nanometer granule, rounded, and smooth in appearance, impurity content is less, diameter Distribution
Uniformly, at about 500nm.Thin wall hollow granule strength is relatively low, occurs in that the situation of breakage.EDS power spectrum illustrates qualitatively
In Li, carbon, nitrogen element, the percentage by weight of tin element are respectively 52.53%, and 19.05%, 28.42%.Thin wall hollow
Stanniferous amount in grain wall is too low, thus causes electrode capacity less than normal.Volumetric expansion in charge and discharge process be easy to by
Particle wall is burst, thus causes the broken of granule, reunites and ultimate failure.
Embodiment 2:
1) being dissolved in 10mL absolute methanol by 20mg catechol monomer, ultrasonic disperse is uniform；By molten for 10mg boronic acid monomer
Liquid is dissolved in 10mL absolute methanol, and ultrasonic disperse is uniform.Drop in the case of catechol monomer solution is stirred at room temperature
In boronic acid monomer solution, add the stannic chloride pentahydrate solution of 10mL 3mg/mL after dropping immediately, at room temperature continue anti-
Answer 8 hours.After reaction terminates, product absolute methanol is cleaned to remove undesired impurities, finally product is dried, in i.e. obtaining
Empty metallo-organic nanoparticle.
2) being placed in tube furnace by prepared hollow metal-organic nanometer granule, under argon shield, 800 DEG C of calcinings 3 are little
Time, obtain hollow tin carbon nanometer granule.
This example prepares thin wall hollow tin carbon nanometer granule, rounded, and smooth in appearance, impurity content is less, diameter Distribution
Uniformly, at about 500nm.EDS power spectrum illustrates the weight percent score of carbon in granule, nitrogen element, tin element qualitatively
It is not 51.62%, 18.35%, 30.03%.Stanniferous amount in thin wall hollow particle wall is too low, thus causes electrode capacity inclined
Little.Volumetric expansion in charge and discharge process is easy to burst particle wall, thus causes the broken of granule, reunites and
Lost efficacy eventually.
Embodiment 3:
1) being dissolved in 10mL absolute methanol by 20mg catechol monomer, ultrasonic disperse is uniform；By molten for 20mg boronic acid monomer
Liquid is dissolved in 10mL absolute methanol, and ultrasonic disperse is uniform.Drop in the case of catechol monomer solution is stirred at room temperature
In boronic acid monomer solution, add the stannic chloride pentahydrate solution of 10mL 4mg/mL after dropping immediately, at room temperature continue anti-
Answer 6 hours.After reaction terminates, product absolute methanol is cleaned to remove undesired impurities, finally product is dried, in i.e. obtaining
Empty metallo-organic nanoparticle.
2) being placed in tube furnace by prepared hollow metal-organic nanometer granule, under argon shield, 1000 DEG C of calcinings 5 are little
Time, obtain hollow tin carbon nanometer granule.
This example prepares thick walled hollow tin carbon nanometer granule, and diameter Distribution is uniform, and at about 500nm, shape is regular, distribution
Uniformly, defects such as reuniting, rupture does not occurs.EDS power spectrum illustrates carbon in granule, nitrogen element, tin element qualitatively
Percentage by weight is respectively 48.31%, and 17.38%, 34.31%.The discharge cycles first of thick walled hollow stannum carbon granule electrode is held
Amount has reached 982mAh g-1, the capacity after this kind of negative material circulates at 100 times drops to 240mAh g-1, capacity keeps
Rate is general, and stable circulation performance is poor.
Embodiment 4:
1) being dissolved in 10mL absolute methanol by 20mg catechol monomer, ultrasonic disperse is uniform；By molten for 20mg boronic acid monomer
Liquid is dissolved in 10mL absolute methanol, and ultrasonic disperse is uniform.Drop in the case of catechol monomer solution is stirred at room temperature
In boronic acid monomer solution, add the stannic chloride pentahydrate solution of 10mL 1.5mg/mL after dropping immediately, at room temperature continue
React 5 hours.After reaction terminates, product absolute methanol is cleaned to remove undesired impurities, finally product is dried, i.e. obtains
Hollow metal-organic nanometer granule.
2) being placed in tube furnace by prepared hollow metal-organic nanometer granule, under argon shield, 700 DEG C of calcinings 2 are little
Time, obtain hollow tin carbon nanometer granule.
This example prepares thin wall hollow tin carbon nanometer granule, rounded, and smooth in appearance, impurity content is less, diameter Distribution
Uniformly, at about 500nm.Thin wall hollow granule strength is relatively low, occurs in that the situation of breakage.EDS power spectrum illustrates qualitatively
In Li, carbon, nitrogen element, the percentage by weight of tin element are respectively 52.03%, and 18.74%, 29.23%.Thin wall hollow
Stanniferous amount in grain wall is too low, thus causes electrode capacity less than normal.Volumetric expansion in charge and discharge process be easy to by
Particle wall is burst, thus causes the broken of granule, reunites and ultimate failure.
Embodiment 5:
1) being dissolved in 10mL absolute methanol by 20mg catechol monomer, ultrasonic disperse is uniform；By molten for 20mg boronic acid monomer
Liquid is dissolved in 10mL absolute methanol, and ultrasonic disperse is uniform.Drop in the case of catechol monomer solution is stirred at room temperature
In boronic acid monomer solution, add the stannic chloride pentahydrate solution of 10mL 10mg/mL after dropping immediately, at room temperature continue
React 10 hours.After reaction terminates, product absolute methanol is cleaned to remove undesired impurities, finally product is dried, to obtain final product
To hollow metal-organic nanometer granule.
2) being placed in tube furnace by prepared hollow metal-organic nanometer granule, under argon shield, 600 DEG C of calcinings 2 are little
Time, obtain hollow tin carbon nanometer granule.
This example prepares hyper-thick pipe hollow tin carbon nanometer granule, and rounded, smooth in appearance, impurity content is less, and diameter divides
Cloth is uniform, at about 500nm.EDS power spectrum illustrates carbon in granule, nitrogen element, the percentage by weight of tin element qualitatively
It is respectively 41.85%, 12.41%, 45.74%.The counteracting force of the granule opposing volumetric expansion of hyper-thick pipe is greatly enhanced, and alleviates
Volumizing effect is inconspicuous, it is impossible to reach its due effect.
Embodiment 6:
1) being dissolved in 10mL absolute methanol by 20mg catechol monomer, ultrasonic disperse is uniform；By molten for 20mg boronic acid monomer
Liquid is dissolved in 10mL absolute methanol, and ultrasonic disperse is uniform.Drop in the case of catechol monomer solution is stirred at room temperature
In boronic acid monomer solution, add the stannic chloride pentahydrate solution of 10mL 5mg/mL after dropping immediately, at room temperature continue anti-
Answer 6 hours.After reaction terminates, product absolute methanol is cleaned to remove undesired impurities, finally product is dried, in i.e. obtaining
Empty metallo-organic nanoparticle.
2) being placed in tube furnace by prepared hollow metal-organic nanometer granule, under argon shield, 800 DEG C of calcinings 2 are little
Time, obtain hollow tin carbon nanometer granule.
In this example, stannic chloride pentahydrate solution concentration is 5mg/mL, prepares thick walled hollow tin carbon nanometer granule, and diameter divides
Cloth is uniform, and at about 500nm, shape is regular, is evenly distributed, and defects such as reuniting, rupture does not occurs.EDS power spectrum is said qualitatively
Understand that in granule, carbon, nitrogen element, the percentage by weight of tin element are respectively 44.74%, 16.08%, 36.18%.Heavy wall
The capacity of discharge cycles first of hollow stannum carbon granule electrode has reached 1044mAh g-1, after this kind of negative material circulates at 250 times
Capacity still up to 480mAh g-1, compared with nanometer tin granule, its capability retention is higher, and stable circulation performance improves aobvious
Write.
Be can be seen that by above six examples, the concentration of stannic chloride pentahydrate solution is the most crucial.When tin ion addition is
The when of many, the granule of gained is almost without producing hollow structure, and when tin ion addition is minimum when, gained
Grain wall thickness is the thinnest.If wall thickness is the thinnest, then the stanniferous amount in particle wall is by too low, thus causes electrode capacity less than normal.If additionally,
Wall thickness is the thinnest, and the Volumetric expansion in charge and discharge process is easy to burst particle wall, thus causes the broken of granule, group
Coalescence ultimate failure.When wall thickness is blocked up, the counteracting force of granule opposing volumetric expansion will be greatly enhanced, particle cavities volume mistake
Little, alleviate volumizing effect inconspicuous, be unable to reach its due effect equally.Select wall thickness in the hollow of 150-200nm
Granule, i.e. tin ion concentration are that the hollow stannum carbon granule obtained by butter of tin methanol solution of 5mg/L is as electro-chemical test
Raw material, capability retention is higher, and cyclical stability is obviously improved.
The capacity of discharge cycles for several times of nanometer tin granule reaches 864mAh g-1, it is reduced to after 100 circulations
90mAh·g-1.Hollow stannum carbon granule diameter Distribution prepared by the present invention is 400-600 nanometer, uniform particle sizes.The nano junction of hollow
Structure alleviates the stannum Volumetric expansion when discharge and recharge to a great extent, and hollow structure is that volumetric expansion provides internal sending out
What the failure conditions such as exhibition space, can reduce particle agglomeration caused when it expands to the periphery as far as possible, powder of detached occurred can
Energy property and the order of severity, thus ensure that the capacity of electrode active material, improve the stability after repeatedly circulation.Secondly, in
The specific surface area of empty stannum carbon granule is bigger, it is provided that the reaction occasion of more embedding/deintercalate lithium ions, and metal-organic
The special construction of framework material is also provided that more electron propagation ducts, can reduce resistance to a certain extent, promotes electrode
The electric conductivity of material.Material with carbon element self-conductive performance and during preparing monomer contained by raw material p-phenylenediamine nitrogen unit
Element causes the natural N doping of the polymer base lifting to the electric conductivity of granule.This product is applied to lithium ion battery negative
Material, assembled battery carries out electrochemical Characterization, and the capacity of discharge cycles first of electrode has reached 1044mAh g-1, at 200mA
g-1Electric current density under through 250 times circulation after still there is 480mAh g-1Capacity, capability retention is preferable, and electrode follows
Ring stability is significantly improved.
Above example is only to be lifted by the explanation present invention, and protection scope of the present invention is not limited to this.The art
The equivalent done on the basis of the present invention of technical staff substitute and conversion, all within protection scope of the present invention.
Claims (3)
1. the preparation method of the stannum carbon composite nano granule of a hollow structure；It is characterized in that step is as follows:
1) be 1:4～3:1 in mass ratio by catechol monomer dropping boronic acid monomer solution extremely in, be subsequently adding 1.5mg
～the stannic chloride pentahydrate solution of 10mg/mL, at room temperature sustained response 5～10 hours；After reaction terminates, by dry for product washing
Dry, obtain hollow metal-organic nanometer granule；
2) being placed in tube furnace by hollow metal-organic nanometer granule, under argon shield, 500～1000 DEG C of calcinings 1～5 are little
Time, obtain hollow tin carbon nanometer granule.
2. the method for claim 1, is characterized in that catechol monomer is 1:2～2:1 with the mass ratio of boronic acid monomer.
3. the stannum carbon composite nano granular materials of hollow structure is used for lithium ion battery negative material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106996946A (en) * | 2017-03-31 | 2017-08-01 | 温州大学 | N doping circle carbon plate and tin-oxide composite and its preparation method and application |
| CN108376774A (en) * | 2018-02-08 | 2018-08-07 | 陕西科技大学 | A kind of sodium-ion battery cathode tin carbon composite hollow ball material and its application |
| CN111540891A (en) * | 2020-05-11 | 2020-08-14 | 中国科学院重庆绿色智能技术研究院 | Preparation method of low-cost high-performance tin-carbon lithium battery negative electrode material |
| CN112794305A (en) * | 2021-01-14 | 2021-05-14 | 西北工业大学 | Preparation method and application of hollow carbon nanosphere confined tin nanocluster composite material |
| CN113707855A (en) * | 2021-08-18 | 2021-11-26 | 大连大学 | Lithium ion battery cathode composite material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102054974A (en) * | 2010-12-07 | 2011-05-11 | 浙江大学 | Preparation method for stannic oxide/carbon composite hollow balls |
| CN103022454A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Preparation method of tin-carbon composite negative electrode material |
| CN103682273A (en) * | 2013-12-11 | 2014-03-26 | 高建军 | Preparation method of tin-carbon composite material of lithium ion battery |
| CN104538605A (en) * | 2014-12-08 | 2015-04-22 | 江西正拓新能源科技股份有限公司 | Tin-carbon composite cathode material and preparation method thereof |
| CN105428614A (en) * | 2015-11-06 | 2016-03-23 | 盐城工学院 | Nitrogen-doped porous composite negative electrode material and preparation method therefor |
| CN105576207A (en) * | 2016-01-28 | 2016-05-11 | 天津大学 | Preparation method and application of hollow tin-copper alloy @ silicon dioxide nuclear shell nanocomposite |
-
2016
- 2016-09-10 CN CN201610815150.7A patent/CN106229490A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102054974A (en) * | 2010-12-07 | 2011-05-11 | 浙江大学 | Preparation method for stannic oxide/carbon composite hollow balls |
| CN103022454A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Preparation method of tin-carbon composite negative electrode material |
| CN103682273A (en) * | 2013-12-11 | 2014-03-26 | 高建军 | Preparation method of tin-carbon composite material of lithium ion battery |
| CN104538605A (en) * | 2014-12-08 | 2015-04-22 | 江西正拓新能源科技股份有限公司 | Tin-carbon composite cathode material and preparation method thereof |
| CN105428614A (en) * | 2015-11-06 | 2016-03-23 | 盐城工学院 | Nitrogen-doped porous composite negative electrode material and preparation method therefor |
| CN105576207A (en) * | 2016-01-28 | 2016-05-11 | 天津大学 | Preparation method and application of hollow tin-copper alloy @ silicon dioxide nuclear shell nanocomposite |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106996946A (en) * | 2017-03-31 | 2017-08-01 | 温州大学 | N doping circle carbon plate and tin-oxide composite and its preparation method and application |
| CN108376774A (en) * | 2018-02-08 | 2018-08-07 | 陕西科技大学 | A kind of sodium-ion battery cathode tin carbon composite hollow ball material and its application |
| CN111540891A (en) * | 2020-05-11 | 2020-08-14 | 中国科学院重庆绿色智能技术研究院 | Preparation method of low-cost high-performance tin-carbon lithium battery negative electrode material |
| CN112794305A (en) * | 2021-01-14 | 2021-05-14 | 西北工业大学 | Preparation method and application of hollow carbon nanosphere confined tin nanocluster composite material |
| CN112794305B (en) * | 2021-01-14 | 2022-10-21 | 西北工业大学 | Preparation method and application of hollow carbon nanosphere confined tin nanocluster composite material |
| CN113707855A (en) * | 2021-08-18 | 2021-11-26 | 大连大学 | Lithium ion battery cathode composite material and preparation method thereof |
| CN113707855B (en) * | 2021-08-18 | 2023-11-07 | 大连大学 | Lithium ion battery negative electrode composite material and preparation method thereof |
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Application publication date: 20161214 |