CN104409708B - A kind of preparation method of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material - Google Patents
A kind of preparation method of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material Download PDFInfo
- Publication number
- CN104409708B CN104409708B CN201410623977.9A CN201410623977A CN104409708B CN 104409708 B CN104409708 B CN 104409708B CN 201410623977 A CN201410623977 A CN 201410623977A CN 104409708 B CN104409708 B CN 104409708B
- Authority
- CN
- China
- Prior art keywords
- graphene
- microsphere
- negative material
- ion battery
- lithium ion
- 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.)
- Active
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 119
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000005253 cladding Methods 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 title claims description 84
- 229910020810 Sn-Co Inorganic materials 0.000 title claims description 72
- 229910018757 Sn—Co Inorganic materials 0.000 title claims description 72
- 239000003610 charcoal Substances 0.000 claims abstract description 51
- 239000002086 nanomaterial Substances 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 238000001694 spray drying Methods 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 28
- 239000011780 sodium chloride Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000000889 atomisation Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- 229910052803 cobalt Inorganic materials 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000003638 reducing agent Substances 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- 125000004429 atoms Chemical group 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910020212 Na2SnO3 Inorganic materials 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J Tin(IV) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 238000007792 addition Methods 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052744 lithium Inorganic materials 0.000 abstract description 16
- 238000003860 storage Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- -1 graphite alkene Chemical class 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000009829 pitch coating Methods 0.000 abstract description 2
- 229910000531 Co alloy Inorganic materials 0.000 abstract 4
- 239000007773 negative electrode material Substances 0.000 abstract 2
- 150000001875 compounds Chemical group 0.000 description 12
- 238000005275 alloying Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000002296 pyrolytic carbon Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 229940063834 Carboxymethylcellulose Sodium Drugs 0.000 description 2
- 229910019043 CoSn Inorganic materials 0.000 description 2
- 229910019050 CoSn2 Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000002427 irreversible Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229910020646 Co-Sn Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L Cobalt(II) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910020709 Co—Sn Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 206010037844 Rash Diseases 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Abstract
Based on Sn Co alloy can have that lithium storage content is high, coulombic efficiency big simultaneously for prior art there is no, have extended cycle life and lithium ion battery negative material that packing density is big, the invention provides the preparation method of a kind of lithium ion battery carbon cladding Sn Co alloy/graphite alkene composite microsphere negative electrode material, belong to lithium ion battery negative material field.Sn Co Nanoalloy is deposited on graphenic surface by wet method by the method, then use spray drying method that nanostructure intermediate is carried out pelletize, again complex microsphere intermediate is carried out pitch-coating, the mode finally carrying out heating carbonization prepares charcoal cladding Sn Co alloy/graphite alkene composite microsphere negative electrode material, and the method preparation technology is simple, be suitable for large-scale industrialized production；The charcoal cladding Sn Co alloy/graphite alkene microsphere negative material lithium storage content that the method prepares is high, coulombic efficiency big, have extended cycle life, packing density is big.
Description
Technical field
The invention belongs to a kind of lithium ion battery negative material field, particularly to a kind of lithium ion battery carbon cladding
The preparation method of Sn-Co/ Graphene microsphere negative material.
Background technology
In recent years, along with electronic information technology develop, multimedia function increases, mobile phone 4G communication function promote with
And electric automobile single charge travels distance and extends.Therefore, existing lithium ion battery increasingly can not meet people
The demand growing to capacity.Negative material is one of key factor affecting capacity of lithium ion battery.At present
The graphite cathode material of large-scale application has the advantages such as efficiency for charge-discharge height, good cycle, but theory stores up lithium
Capacity is low, and specific discharge capacity is 372mAh/g, and volume and capacity ratio is 800mAh/cm3, actual capacity has connect
Nearly theoretical capacity, improves space little.The Theoretical Mass specific capacity of metallic tin is 990mAh/g, especially volume
Specific capacity reaches 7200mAh/cm3, the always focus of cathode material for high capacity lithium ion battery research.But it is this kind of
Material volumetric expansion in charge and discharge process reaches 3～4 times, and crystal structure is more easily damaged and final efflorescence, makes to follow
Ring degradation, seriously hinders the extensive industrialization of Sn base negative material.
To this end, people mainly use the approach such as granule nanorize, alloying and Composite to reduce Sn sill
Volumetric expansion, improve cycle performance.The nanorize of metal Sn can significantly reduce particle volume and expand generation
Internal stress, reduce volumetric expansion multiple, make cycle performance be improved significantly.But the filling of nano material is close
Spending little, specific surface area and surface can be big, cause volume and capacity ratio low and coulombic efficiency is low.Metal Sn and activity unit
Element or the alloying of inert element can reduce volumetric expansion multiple, improve cycle performance, and wherein the inertia such as Co is closed
Gold element is as itself being not involved in reaction, and skeletal support effect is more preferable.Sn-Co alloy is compound with carbon, boron and phosphorus etc.
Change can buffer the volumetric expansion of alloy, simultaneously works as compartmentation and prevents Nanoalloy from reuniting, improves material
Cycle performance.But, up to the present, people the most do not invent a kind of based on Sn-Co alloy can be with
Time have that lithium storage content is high, coulombic efficiency big, have extended cycle life and lithium ion battery negative material that packing density is big
Material.
Summary of the invention
In order to solve the problems referred to above, the present invention proposes a kind of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere
The preparation method of negative material.Sn-Co Nanoalloy is deposited on graphenic surface by wet method and is formed by the method
Nanostructure intermediate, then uses spray drying method that nanostructure intermediate carries out pelletize and forms complex microsphere intermediate,
Complex microsphere intermediate carries out pitch-coating again, and the mode finally carrying out heating carbonization prepares charcoal cladding
Sn-Co/ Graphene microsphere negative material, the method preparation technology is simple, be suitable for large-scale industrialized production；The party
The charcoal cladding Sn-Co/ Graphene microsphere negative material lithium storage content that method prepares is high, coulombic efficiency is big, cycle life
Length, packing density are big.
For achieving the above object, technical solution of the present invention is as follows:
The preparation method of a kind of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material, comprises following step
Rapid:
(1) nanostructure intermediate is prepared: solubility Sn salt and solubility Co salt are added deionized water, fully dissolves
After, add Graphene and surface modifier solution, after ultrasonic disperse 5～10min, add reducing agent reaction
10～20min, the Sn-Co Nanoalloy that reaction generates is deposited on graphenic surface, is filtered by reaction solution, again
Solid matter is washed, is dried, obtain nanostructure intermediate；
Wherein, described Graphene is through the oxidation of Hummer method and hydrazine hydrate reduction system by natural flake graphite
, there is atomic structure of carbon defect and the monolayer of surface functional group or less than few layer graphene of 10 layers；
Solubility Sn salt is SnCl4, SnSO4, Na2SnO3Or Sn2P2O7, solubility Co salt is CoSO4
Or Co (NO3)2；Reducing agent is the NaBH of 0.1～1mol/L4Ethanol solution or KBH4Aqueous solution；Surface modification
Agent is sodium lauryl sulphate or dodecyl sodium sulfate；
Solubility Sn salt with the additional proportion of solubility Co salt is: with Sn, Co atom in Sn salt and Co salt
Meter, Sn accounts for the 65～80% of Sn, Co gross mass；Sn salt and Co salt gross mass with the rate of charge of deionized water are
1g:5～30mL；Graphene quality is (0.5～10) with the ratio of Sn, Co atom gross mass in Sn salt and Co salt:
(60～98.5)；Surface modifier quality is the 2～5% of deionized water quality；The molal quantity of reducing agent is Sn salt
Middle Sn ion and Co ion in quantivalence sum of products Co salt and the quantivalence sum of products
1.1～1.5 times；
(2) complex microsphere intermediate is prepared: by the nanostructure intermediate of step (1) gained adds deionized water, stir
Mix after uniformly, add binding agent, stir into slurry, be then 110～180 DEG C in inlet temperature, outlet temperature
Being 80～95 DEG C, atomisation pressure is 0.5～2MPa, and nozzle diameter is to carry out spray dried under conditions of 0.3～0.7mm
Dry pelletize, obtaining particle diameter is micron-sized complex microsphere intermediate bulky grain；
Wherein, nanostructure intermediate is 10g:(5～15 with the solid-to-liquid ratio of deionized water) mL, nanostructure intermediate is with viscous
The mass ratio of knot agent is 10:(1～3)；
Described binding agent is starch, polyvinyl alcohol or sodium carboxymethyl cellulose；
(3) prepare charcoal covered composite yarn microsphere: added by asphalt in kerosene, after fully dissolving, add step
(2) the complex microsphere intermediate of gained, heating, drying at speed stirs 50～100rpm, temperature 200～280 DEG C,
Last carrying out under the inert gas atmosphere such as nitrogen or argon heats carbonization, obtains charcoal cladding Sn-Co/ Graphene micro-
Ball；
Wherein, the matter of Graphene in the complex microsphere intermediate obtained in described asphalt addition and step (2)
Amount ratio is (1～30): (0.5～10)；
Described carbonization heating cycle is: with the ramp of 2～10 DEG C/min to after 600-1500 DEG C, insulation
0.5～5h, then furnace cooling.
After tested, charcoal cladding Sn-Co/ Graphene microsphere negative material prepared by the present invention, the most embedding lithium capacity is
332～645mAh/g, efficiency for charge-discharge is 80.6～90.3%, circulates the discharge capacity after 50 times and is
303～497mAh/g.
Scanned electron microscopic observation, the granularity of microsphere negative material prepared by the present invention is 20～60 μm, microsphere top layer
The compound layer of charcoal formed with pyrolytic carbon for Graphene, is the loose structure being separated to form by Graphene inside microsphere,
Pore interior at loose structure deposits the Sn-Co alloying pellet having particle diameter to be 40～100nm.
The present invention has a following remarkable advantage relative to prior art:
1, the charcoal cladding Sn-Co/ Graphene microsphere negative material prepared by the present invention, overcomes existing nanoscale
It is low to there is packing density in Sn-Co alloy, the shortcoming that volume and capacity ratio is little.The present invention with starch, polyvinyl alcohol or
Sodium carboxymethyl cellulose, as binding agent, uses spray drying granulation method to obtain micron-size spherical particles, it is possible to have
Effect improves packing density, it is thus achieved that high volume and capacity ratio.
2, the charcoal cladding Sn-Co/ Graphene microsphere negative material prepared by the present invention, overcomes existing graphite
Sn-Co alloy can not be separated and reserve by the complex carrier such as grain, organic matter pyrolysis charcoal, Carbon fibe effectively
Expansion space, the shortcoming causing cycle performance prompting weak effect.Graphene is a kind of by monolayer carbon atomic building
Two-dimensional material, has the intensity of superelevation, good pliability, excellent electrical conductivity and self can store Li,
The present invention is with Graphene as carrier, and Graphene can effectively be separated to form loose structure, for Sn-Co Nanoalloy
Expand reserved elastic space, and Sn-Co Nanoalloy is played good supporting function, not only contribute to
The capacity of Sn-Co alloy plays the raising with cycle performance and improves negative pole whole volume and electron conduction.
3, the charcoal cladding Sn-Co/ Graphene microsphere negative material prepared by the present invention, overcomes existing Sn-Co/C
It is relatively big to there is specific surface area in composite, and irreversible capacity is high, the shortcoming that efficiency for charge-discharge is low.The present invention is with drip
Blue or green as carbon precursor covered composite yarn microsphere particle, the compound layer of charcoal of formation can play stable particle structure and fall
Low granule exposes the dual function of surface area in the electrolytic solution, reduces irreversible capacity, improves first charge-discharge effect
Rate and cycle performance.
4, the charcoal cladding Sn-Co/ Graphene microsphere negative material prepared by the present invention, Co-Sn Nanoalloy by
CoSn and CoSn2Phase composition, wherein CoSn2Having higher capacity, CoSn has preferable cycle performance,
The Sn-Co alloy of the two compound composition has had good capacity and cycle performance concurrently.
5, the present invention uses the method that liquid deposition, pelletize, surrounding phase combine, and technique is simple, it is extensive to be suitable for
Industrialization produces.
Therefore, the preparation side of the charcoal cladding Sn-Co/ Graphene microsphere negative material of a kind of lithium ion battery of the present invention
Method, it is thus achieved that microsphere negative material to have lithium storage content high, coulombic efficiency is big, has extended cycle life and packing density
The advantage such as big, meets the requirement of high performance lithium ion battery anticathode material combination property.
Accompanying drawing explanation
Fig. 1 is the charcoal cladding Sn-Co/ Graphene microsphere negative material of the lithium ion battery prepared in embodiment 1
Electron-microscope scanning figure.
Detailed description of the invention
In embodiment, the preparation method of Graphene is: take the dense H of 18～25mL98%2SO4Add and be placed in ice bath
Reactor in, by natural flake graphite that 1～1.5g granularity is 10～30 μm and the KMnO of 3～4g4Add
In reactor, with 30～80rpm rotating speed stirrings 30～60min；Above-mentioned reactor is moved into the warm water of 40 ± 2 DEG C again
Bath continues stirring 30～60min；Again reacting liquid temperature is increased to 98 ± 2 DEG C, adds 70～100mL deionizations
Water continues stirring 30～60min；Being subsequently adding 8～15mL mass fractions is the H of 5%2O2Mix homogeneously, while hot
Filter, wash filtering residue with the HCl that mass fraction is 5%, until without SO in filtrate4 2-(use BaC12Solution is examined
Survey), more fully wash with deionized water to neutrality, filter, obtain graphite oxide；Then add to graphite oxide
400～500mL deionized waters, with 60kHz supersound process 60～90min at 80～90 DEG C, then with
3000～4000rpm rotating speeds are centrifuged 5～10min；Take supernatant, add the hydrazine hydrate aqueous solution of 0.5～1g50%,
In 85～95 DEG C of reduction reactions 60～120min, filter, precipitate is put into 50～70 DEG C of oven dryings 60～80h.
Other reagent are commercial.
It is described in further detail below in conjunction with specific embodiment, but the present invention is not limited thereto.
Embodiment 1
1, nanostructure intermediate is prepared: by the SnCl of 26.07g4CoSO with 16.79g4Add 1286mL to go
Ionized water, after fully dissolving, adds 92.7mg Graphene and 25.7g sodium lauryl sulphate, ultrasonic disperse
After 5min, add the NaBH of 1mol/L4Ethanol solution 925mL, reacts 20min, at graphenic surface
Deposition Sn-Co Nanoalloy, reaction solution, through filtering, washed by solid matter, being dried, obtains in the middle of nanometer
Body；
2, complex microsphere intermediate is prepared: the nanostructure intermediate prepare step 1 adds 15mL in every 10g
Deionized water, after stirring, then adds 3g starch in every 10g nanostructure intermediate, stirs into slurry, adopt
Carrying out pelletize by spray drying granulation method, inlet temperature is 110 DEG C, and outlet temperature is 80 DEG C, and atomisation pressure is
0.5MPa, nozzle diameter is 0.7mm, obtains complex microsphere intermediate；
3, charcoal covered composite yarn microsphere is prepared: added in 10mL kerosene solvent by 185.4mg Colophonium, fully dissolve
After, add the complex microsphere intermediate of step 2 gained, stir post-drying, finally at N2Under atmosphere,
Being warming up to 600 DEG C from room temperature by 2 DEG C/min, insulation 0.5h carries out carbonization, obtains charcoal cladding Sn-Co/ Graphene
Microsphere.
By gained charcoal cladding Sn-Co/ Graphene microsphere, conductive agent acetylene black and binding agent PVDF according to quality hundred
Proportion by subtraction 85:5:10 mixes, and makes electrode slice, is to electrode by metal lithium sheet, 1mol/L's
LiPF6/ EC+DMC+DEC is that electrolyte is assembled into half-cell.Use Shenzhen new Weir battery test system half-and-half
Battery at room temperature carries out constant current charge-discharge test, and charging or discharging current is 0.05mA/cm2, voltage range is
0.01-1.5V.The most embedding lithium capacity of the charcoal cladding Sn-Co/ Graphene microsphere negative material of preparation is
320mAh/g, efficiency for charge-discharge is 80.6%, and circulating the discharge capacity after 50 times is 303mAh/g.
Scanned electron microscopic observation, the granularity of this microsphere negative material is 20～60 μm, microsphere top layer be Graphene with
The compound layer of charcoal that pyrolytic carbon is formed, is the loose structure being separated to form by Graphene inside microsphere, at loose structure
Pore interior deposit have particle diameter to be 40～100nm Sn-Co alloying pellet.Shown in Fig. 1 for this negative pole material
The outward appearance scanning electron microscope (SEM) photograph of material.
Embodiment 2
1, nanostructure intermediate is prepared: by the SnSO of 42.94g4CoSO with 33.58g4Add 1377mL to go
Ionized water, after fully dissolving, adds 6.09g Graphene and 48.2g sodium lauryl sulphate, ultrasonic disperse
After 10min, add the KBH of 0.5mol/L4Aqueous solution 2467mL, reacts 10min, at graphenic surface
Deposition Sn-Co Nanoalloy, reaction solution, through filtering, washed by solid matter, being dried, obtains in the middle of nanometer
Body；
2, complex microsphere intermediate is prepared: the nanostructure intermediate prepare step 1 adds 5mL in every 10g
Deionized water, after stirring, then adds 1g polyvinyl alcohol in every 10g nanostructure intermediate, stirs into slurry,
Using spray drying granulation method to carry out pelletize, inlet temperature is 140 DEG C, and outlet temperature is 87 DEG C, atomisation pressure
For 1.5MPa, nozzle diameter is 0.5mm, obtains complex microsphere intermediate；
3, charcoal covered composite yarn microsphere is prepared: added in 200mL kerosene solvent by 18.26g Colophonium, fully dissolve
After, adding the complex microsphere intermediate of step 2 gained, stirring and drying, the most under an argon atmosphere, from room
Temperature is warming up to 1500 DEG C by 10 DEG C/min, and insulation 5h carries out carbonization, obtains charcoal cladding Sn-Co/ Graphene microsphere.
Record the most embedding lithium of the charcoal cladding Sn-Co/ Graphene microsphere negative material of preparation as described in Example 1
Capacity is 620mAh/g, and efficiency for charge-discharge is 86.6%, and circulating the discharge capacity after 50 times is 453mAh/g.
Scanned electron microscopic observation, the granularity of this microsphere negative material is 20～60 μm, microsphere top layer be Graphene with
The compound layer of charcoal that pyrolytic carbon is formed, is the loose structure being separated to form by Graphene inside microsphere, at loose structure
Pore interior deposit have particle diameter to be 40～100nm Sn-Co alloying pellet.
Embodiment 3
1, nanostructure intermediate is prepared: by the Na of 21.27g2SnO3Co (NO with 19.82g3)2Join
205mL deionized water, after fully dissolving, adds 1.14g Graphene and 10.3g dodecyl sodium sulfate, super
After sound dispersion 8min, add the NaBH of 0.1mol/L4Ethanol solution 8016mL, reacts 15min, at stone
Ink alkene surface deposition Sn-Co Nanoalloy, reaction solution, through filtering, washed by solid matter, being dried, obtains
Nanostructure intermediate；
2, complex microsphere intermediate is prepared: the nanostructure intermediate prepare step 1 adds 10mL in every 10g
Deionized water, after stirring, then adds 2g Carboxymethyl cellulose sodium, stirring in every 10g nanostructure intermediate
Form slurry, uses spray drying granulation method to carry out pelletize, and inlet temperature is 180 DEG C, and outlet temperature is 95 DEG C,
Atomisation pressure is 2MPa, and nozzle diameter is 0.3mm, obtains complex microsphere intermediate；
3, charcoal covered composite yarn microsphere is prepared: added by 3.4g Colophonium in 50mL kerosene solvent, after fully dissolving,
Adding the complex microsphere intermediate of 10g step 2 gained, stirring and drying, finally at N2Under atmosphere, from room temperature
Being warming up to 1050 DEG C by 6 DEG C/min, insulation 3h carries out carbonization, obtains charcoal cladding Sn-Co/ Graphene microsphere.
Record the most embedding lithium of the charcoal cladding Sn-Co/ Graphene microsphere negative material of preparation as described in Example 1
Capacity is 401mAh/g, and efficiency for charge-discharge is 83.6%, and circulating the discharge capacity after 50 times is 356mAh/g.
Scanned electron microscopic observation, the granularity of this microsphere negative material is 20～60 μm, microsphere top layer be Graphene with
The compound layer of charcoal that pyrolytic carbon is formed, is the loose structure being separated to form by Graphene inside microsphere, at loose structure
Pore interior deposit have particle diameter to be 40～100nm Sn-Co alloying pellet.
Embodiment 4
1, nanostructure intermediate is prepared: by the Sn of 20.57g2P2O7Co (NO with 9.20g3)2Add 893mL
Deionized water, after fully dissolving, adds 75.3mg Graphene and 17.9g dodecyl sodium sulfate, ultrasonic point
After dissipating 5min, add the KBH of 1mol/L4Aqueous solution 451mL, reacts 20min, at graphenic surface
Deposition Sn-Co Nanoalloy, reaction solution, through filtering, washed by solid matter, being dried, obtains in the middle of nanometer
Body；
2, complex microsphere intermediate is prepared: the nanostructure intermediate prepare step 1 adds 15mL in every 10g
Deionized water, after stirring, then adds 3g Carboxymethyl cellulose sodium, stirring in every 10g nanostructure intermediate
Form slurry, uses spray drying granulation method to carry out pelletize, and inlet temperature is 160 DEG C, and outlet temperature is 85 DEG C,
Atomisation pressure is 1MPa, and nozzle diameter is 0.6mm, obtains complex microsphere intermediate；
3, charcoal covered composite yarn microsphere is prepared: added in 10mL kerosene solvent by 150.6mg Colophonium, fully dissolve
After, adding the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N2Under atmosphere, from room temperature
Being warming up to 600 DEG C by 2 DEG C/min, insulation 0.5h carries out carbonization, obtains charcoal cladding Sn-Co/ Graphene microsphere.
Record the most embedding lithium of the charcoal cladding Sn-Co/ Graphene microsphere negative material of preparation as described in Example 1
Capacity is 645mAh/g, and efficiency for charge-discharge is 84.3%, and circulating the discharge capacity after 50 times is 497mAh/g.
Scanned electron microscopic observation, the granularity of this microsphere negative material is 20～60 μm, microsphere top layer be Graphene with
The compound layer of charcoal that pyrolytic carbon is formed, is the loose structure being separated to form by Graphene inside microsphere, at loose structure
Pore interior deposit have particle diameter to be 40～100nm Sn-Co alloying pellet.
Embodiment 5
1, nanostructure intermediate is prepared: by the SnSO of 21.47g4CoSO with 7.80g4Add 526.8mL to go
Ionized water, after fully dissolving, adds 2.47g Graphene and 18.4g sodium lauryl sulphate, ultrasonic disperse
After 10min, add the KBH of 0.5mol/L4Aqueous solution 661mL, reacts 10min, at graphenic surface
Deposition Sn-Co Nanoalloy, reaction solution, through filtering, washed by solid matter, being dried, obtains in the middle of nanometer
Body；
2, complex microsphere intermediate is prepared: the nanostructure intermediate prepare step 1 adds 5mL in every 10g
Deionized water, after stirring, then adds 1g polyvinyl alcohol in every 10g nanostructure intermediate, stirs into slurry,
Using spray drying granulation method to carry out pelletize, inlet temperature is 160 DEG C, and outlet temperature is 85 DEG C, atomisation pressure
For 1MPa, nozzle diameter is 0.6mm, obtains complex microsphere intermediate；
3, charcoal covered composite yarn microsphere is prepared: added by 7.42g Colophonium in 100mL kerosene solvent, after fully dissolving,
Adding the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N2Under atmosphere, press from room temperature
10 DEG C/min is warming up to 1500 DEG C, and insulation 5h carries out carbonization, obtains charcoal cladding Sn-Co/ Graphene microsphere.
Record the most embedding lithium of the charcoal cladding Sn-Co/ Graphene microsphere negative material of preparation as described in Example 1
Capacity is 332mAh/g, and efficiency for charge-discharge is 87.6%, and circulating the discharge capacity after 50 times is 301mAh/g.
Scanned electron microscopic observation, the granularity of this microsphere negative material is 20～60 μm, microsphere top layer be Graphene with
The compound layer of charcoal that pyrolytic carbon is formed, is the loose structure being separated to form by Graphene inside microsphere, at loose structure
Pore interior deposit have particle diameter to be 40～100nm Sn-Co alloying pellet.
Embodiment 6
1, nanostructure intermediate is prepared: by the SnCl of 26.07g4Co (NO with 9.20g3)2Add 176mL
Deionized water, after fully dissolving, adds 927.3mg Graphene and 8.8g dodecyl sodium sulfate, ultrasonic point
After dissipating 8min, add the NaBH of 0.1mol/L4Ethanol solution 6508mL, reacts 15min, at Graphene
Surface deposition Sn-Co Nanoalloy, reaction solution, through filtering, washed by solid matter, being dried, obtains nanometer
Intermediate；
2, complex microsphere intermediate is prepared: the nanostructure intermediate prepare step 1 adds 10mL in every 10g
Deionized water, after stirring, then adds 2g starch in every 10g nanostructure intermediate, stirs into slurry, adopt
Carrying out pelletize by spray drying granulation method, inlet temperature is 180 DEG C, and outlet temperature is 95 DEG C, and atomisation pressure is
2MPa, nozzle diameter is 0.3mm, obtains complex microsphere intermediate；
3, charcoal covered composite yarn microsphere is prepared: added by 2.78g Colophonium in 50mL kerosene solvent, after fully dissolving,
Adding the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N2Under atmosphere, press from room temperature
6 DEG C/min is warming up to 1050 DEG C, and insulation 3h carries out carbonization, obtains charcoal cladding Sn-Co/ Graphene microsphere.
Record the most embedding lithium of the charcoal cladding Sn-Co/ Graphene microsphere negative material of preparation as described in Example 1
Capacity is 353mAh/g, and efficiency for charge-discharge is 90.3%, and circulating the discharge capacity after 50 times is 311mAh/g.
Scanned electron microscopic observation, the granularity of this microsphere negative material is 20～60 μm, microsphere top layer be Graphene with
The compound layer of charcoal that pyrolytic carbon is formed, is the loose structure being separated to form by Graphene inside microsphere, at loose structure
Pore interior deposit have particle diameter to be 40～100nm Sn-Co alloying pellet.
Embodiment 7
1, nanostructure intermediate is prepared: by the Na of 42.54g2SnO3CoSO with 24.25g4Add 1670mL
Deionized water, after fully dissolving, adds 167.4mg Graphene and 66.8g dodecyl sodium sulfate, ultrasonic
After dispersion 6min, add the NaBH of 0.8mol/L4Ethanol solution 2087mL, reacts 18min, at graphite
Alkene surface deposition Sn-Co Nanoalloy, reaction solution, through filtering, washed by solid matter, being dried, is received
Rice intermediate；
2, complex microsphere intermediate is prepared: the nanostructure intermediate prepare step 1 adds 13mL in every 10g
Deionized water, after stirring, then adds 2.5g polyvinyl alcohol in every 10g nanostructure intermediate, stirs pulping
Material, uses spray drying granulation method to carry out pelletize, and inlet temperature is 140 DEG C, and outlet temperature is 87 DEG C, spraying
Pressure is 1.5MPa, and nozzle diameter is 0.5mm, obtains complex microsphere intermediate；
3, charcoal covered composite yarn microsphere is prepared: added in 10mL kerosene solvent by 334.7mg Colophonium, fully dissolve
After, adding the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N2Under atmosphere, from room temperature
Being warming up to 800 DEG C by 3 DEG C/min, insulation 1h carries out carbonization, obtains charcoal cladding Sn-Co/ Graphene microsphere.
Record the most embedding lithium of the charcoal cladding Sn-Co/ Graphene microsphere negative material of preparation as described in Example 1
Capacity is 344mAh/g, and efficiency for charge-discharge is 89.1%, and circulating the discharge capacity after 50 times is 308mAh/g.
Scanned electron microscopic observation, the granularity of this microsphere negative material is 20～60 μm, microsphere top layer be Graphene with
The compound layer of charcoal that pyrolytic carbon is formed, is the loose structure being separated to form by Graphene inside microsphere, at loose structure
Pore interior deposit have particle diameter to be 40～100nm Sn-Co alloying pellet.
Embodiment 8
1, nanostructure intermediate is prepared: by the Sn of 41.14g2P2O7Co (NO with 28.64g3)2Add 1396mL
Deionized water, after fully dissolving, adds 5.50g Graphene and 41.9g sodium lauryl sulphate, ultrasonic disperse
After 9min, add the KBH of 0.2mol/L4Aqueous solution 4278mL, reacts 11min, at graphenic surface
Deposition Sn-Co Nanoalloy, reaction solution, through filtering, washed by solid matter, being dried, obtains in the middle of nanometer
Body；
2, complex microsphere intermediate is prepared: the nanostructure intermediate prepare step 1 adds 6mL in every 10g
Deionized water, after stirring, then adds 1.5g starch in every 10g nanostructure intermediate, stirs into slurry,
Using spray drying granulation method to carry out pelletize, inlet temperature is 110 DEG C, and outlet temperature is 80 DEG C, atomisation pressure
For 0.5MPa, nozzle diameter is 0.7mm, obtains complex microsphere intermediate；
3, charcoal covered composite yarn microsphere is prepared: added in 200mL kerosene solvent by 16.49g Colophonium, fully dissolve
After, adding the complex microsphere intermediate of step 2 gained, stirring and drying, finally at N2Under atmosphere, from room temperature
Being warming up to 1300 DEG C by 8 DEG C/min, insulation 4h carries out carbonization, obtains charcoal cladding Sn-Co/ Graphene microsphere.
Record the most embedding lithium of the charcoal cladding Sn-Co/ Graphene microsphere negative material of preparation as described in Example 1
Capacity is 332mAh/g, and efficiency for charge-discharge is 87.6%, and circulating the discharge capacity after 50 times is 301mAh/g.
Scanned electron microscopic observation, the granularity of this microsphere negative material is 20～60 μm, microsphere top layer be Graphene with
The compound layer of charcoal that pyrolytic carbon is formed, is the loose structure being separated to form by Graphene inside microsphere, at loose structure
Pore interior deposit have particle diameter to be 40～100nm Sn-Co alloying pellet.
Claims (9)
1. a preparation method for lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material, its feature exists
In, comprise the steps of
(1) nanostructure intermediate is prepared
Solubility Sn salt and solubility Co salt are added deionized water, after fully dissolving, adds Graphene and table
Face modifier solution, after ultrasonic disperse 5～10min, adds reducing agent reaction 10～20min, and reaction generates
Sn-Co Nanoalloy is deposited on graphenic surface, is filtered by reaction solution, is washed by solid matter, is dried,
Obtain nanostructure intermediate；
Wherein, described Graphene is through the oxidation of Hummer method and hydrazine hydrate reduction system by natural flake graphite
, there is atomic structure of carbon defect and the monolayer of surface functional group or less than few layer graphene of 10 layers；Solvable
Property Sn salt is SnCl4, SnSO4, Na2SnO3Or Sn2P2O7；Solubility Co salt is CoSO4Or Co (NO3)2；
Reducing agent is the NaBH of 0.1～1mol/L4Ethanol solution or KBH4Aqueous solution；Surface modifier is dodecyl
Sodium sulfate or dodecyl sodium sulfate；
(2) complex microsphere intermediate is prepared
The nanostructure intermediate of step (1) gained will add deionized water, after stirring, add binding agent,
Stirring into slurry, then carry out spray drying granulation, obtaining particle diameter is big of micron-sized complex microsphere intermediate
Grain；
(3) charcoal covered composite yarn microsphere is prepared
Asphalt is added in kerosene, after fully dissolving, add in the middle of the complex microsphere of step (2) gained
Body, heating, drying, carry out the most under an inert atmosphere heating carbonization, obtain charcoal cladding Sn-Co/ Graphene microsphere.
A kind of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material the most according to claim 1
Preparation method, it is characterised in that in described step (1), solubility Sn salt adds with solubility Co salt
Entering ratio is: in terms of Sn, Co atom in Sn salt and Co salt, and Sn accounts for the 65～80% of Sn, Co gross mass；
The rate of charge of Sn salt and Co salt gross mass and deionized water is 1g: 5～30mL；Graphene quality and Sn salt and
In Co salt, the ratio of Sn, Co atom gross mass is (0.5～10): (60～98.5)；Surface modifier quality is
The 2～5% of deionized water quality；The molal quantity of reducing agent is Sn ion and quantivalence product in Sn salt
With Co ion in Co salt and the quantivalence sum of products 1.1～1.5 times.
A kind of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material the most according to claim 1
Preparation method, it is characterised in that in step (2), described binding agent is starch, polyvinyl alcohol or carboxylic first
Base sodium cellulosate.
A kind of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material the most according to claim 1
Preparation method, it is characterised in that in step (2), the solid-to-liquid ratio of described nanostructure intermediate and deionized water
For 10g: (5～15) mL, nanostructure intermediate is 10 with the mass ratio of binding agent: (1～3).
A kind of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material the most according to claim 1
Preparation method, it is characterised in that the spray drying granulation condition described in step (2) is: inlet temperature is
110～180 DEG C, outlet temperature is 80～95 DEG C, and atomisation pressure is 0.5～2MPa, and nozzle diameter is 0.3～0.7mm.
A kind of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material the most according to claim 1
Preparation method, it is characterised in that in step (3), in described asphalt addition and step (2)
To complex microsphere intermediate in the mass ratio of Graphene be (1～30): (0.5～10).
A kind of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material the most according to claim 1
Preparation method, it is characterised in that in step (3), described heating, drying condition is: speed stir
50～100rpm, drying temperature 200～280 DEG C.
A kind of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material the most according to claim 1
Preparation method, it is characterised in that in step (3), described carbonization heating cycle is: with 2～10 DEG C/min
Ramp to after 600～1500 DEG C, be incubated 0.5～5h, then furnace cooling；Described inert atmosphere is nitrogen
Or argon.
9. lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material, it is characterised in that for according to
The lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material that method described in claim 1 prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410623977.9A CN104409708B (en) | 2014-11-07 | A kind of preparation method of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410623977.9A CN104409708B (en) | 2014-11-07 | A kind of preparation method of lithium ion battery carbon cladding Sn-Co/ Graphene microsphere negative material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104409708A CN104409708A (en) | 2015-03-11 |
| CN104409708B true CN104409708B (en) | 2017-01-04 |
Family
ID=
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800849A (en) * | 2012-07-23 | 2012-11-28 | 浙江大学 | Transition metal tin compound/graphene composite material and preparation method and application thereof |
| CN103715406A (en) * | 2014-01-13 | 2014-04-09 | 中国科学院宁波材料技术与工程研究所 | Preparation and applications of tin based alloy-carbon composite anode active material |
| CN104064739A (en) * | 2014-07-02 | 2014-09-24 | 长沙国容新能源有限公司 | Tin cobalt alloy/ graphene composite material and preparation method thereof |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800849A (en) * | 2012-07-23 | 2012-11-28 | 浙江大学 | Transition metal tin compound/graphene composite material and preparation method and application thereof |
| CN103715406A (en) * | 2014-01-13 | 2014-04-09 | 中国科学院宁波材料技术与工程研究所 | Preparation and applications of tin based alloy-carbon composite anode active material |
| CN104064739A (en) * | 2014-07-02 | 2014-09-24 | 长沙国容新能源有限公司 | Tin cobalt alloy/ graphene composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | N, O co-doped chlorella-based biomass carbon modified separator for lithium-sulfur battery with high capacity and long cycle performance | |
| CN103199254B (en) | A kind of graphite negative material of lithium ion battery and preparation method thereof | |
| Liu et al. | Facile high-voltage sputtering synthesis of three-dimensional hierarchical porous nitrogen-doped carbon coated Si composite for high performance lithium-ion batteries | |
| Li et al. | A Facile Strategy to Construct Silver‐Modified, ZnO‐Incorporated and Carbon‐Coated Silicon/Porous‐Carbon Nanofibers with Enhanced Lithium Storage | |
| Lyu et al. | Carbon/lithium composite anode for advanced lithium metal batteries: Design, progress, in situ characterization, and perspectives | |
| CN109216686A (en) | A kind of lithium ion battery silicon-carbon composite material and preparation method | |
| CN103943860B (en) | Lithium ion power and energy-storage battery negative material and preparation method thereof and battery | |
| CN104591177B (en) | Method for preparing self-supporting three-dimensional porous graphene composite microsphere | |
| CN111573743B (en) | Double-layer hollow dodecahedron zinc-cobalt-based sulfide composite material and preparation method thereof | |
| CN103208625A (en) | Preparation method of ferroferric-oxide-based high-performance negative electrode material for lithium ion battery | |
| Zhou et al. | Scalable synthesis of Si/SiO2@ C composite from micro-silica particles for high performance lithium battery anodes | |
| CN105489854A (en) | Preparation method of high-capacity anode material | |
| CN103035879A (en) | Positive pole piece for lithium-sulfur batteries and preparation method thereof | |
| CN106848220B (en) | A kind of preparation method of graphene-iron oxide-graphene composite structure cell negative electrode material | |
| Huo et al. | Two-dimensional Ti 3 C 2 T x@ S as cathode for room temperature sodium-sulfur batteries | |
| CN105489840A (en) | Silicon-based anode material of lithium ion battery and preparation method of silicon-based anode material | |
| Chen et al. | Synergistic effect of cerium oxide with core-shell structure embedded in porous carbon for high-performance lithium-sulfur batteries | |
| Duan et al. | MOF-71 derived layered Co-CoP/C for advanced Li-S batteries | |
| Li et al. | Architecture and performance of Si/C microspheres assembled by nano-Si via electro-spray technology as stability-enhanced anodes for lithium-ion batteries | |
| Du et al. | Encapsulating yolk-shelled Si@ Co9S8 particles in carbon fibers to construct a free-standing anode for lithium-ion batteries | |
| Qian et al. | ZIF-8/Ketjen Black derived ZnO/N/KB composite for separator modification of lithium sulfur batteries | |
| Wang et al. | ‘Two Birds with One Stone’design for dendrite-free zinc-metal anodes: Three-dimensional highly conductive skeletons loaded with abundant zincophilic sites | |
| Li et al. | Construction of a novel three-dimensional porous lead-carbon network for improving the reversibility of deep discharge lead-carbon batteries | |
| Kim et al. | Vanadium nitride and carbon nanofiber composite membrane as an interlayer for extended life cycle lithium-sulphur batteries | |
| Fu et al. | The surface coating strategy enhances the lithium storage performance of Ni3S2@ PPy self-supporting as anode materials for lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xue Xili Inventor after: Xue Minghu Inventor after: Wang Xinjiang Inventor after: Yang Shaobin Inventor before: Shen Ding Inventor before: Yang Shaobin Inventor before: Dong Wei Inventor before: Wang Xiaoliang Inventor before: Li Sinan Inventor before: Meng Yang |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20170726 Address after: 222300, Jiangsu, Lianyungang province Donghai County Green Town resident Patentee after: LIANYUNGANG JIANGLIDA MINERAL CO., LTD. Address before: Fuxin City, Liaoning Province, China Road 123000 Xihe District No. 47 Patentee before: Liaoning Technical University |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20190307 Address after: 222321 No. 19 Qingfeng Road, Qinghu Town Industrial Concentration Zone, Donghai County, Lianyungang City, Jiangsu Province Patentee after: Jiangsu Jiaming Carbon New Materials Co., Ltd. Address before: 222300 Residence of Qinghu Town, Donghai County, Lianyungang City, Jiangsu Province Patentee before: LIANYUNGANG JIANGLIDA MINERAL CO., LTD. |