CN108682829A - A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material - Google Patents
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material Download PDFInfo
- Publication number
- CN108682829A CN108682829A CN201810592149.1A CN201810592149A CN108682829A CN 108682829 A CN108682829 A CN 108682829A CN 201810592149 A CN201810592149 A CN 201810592149A CN 108682829 A CN108682829 A CN 108682829A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped carbon
- organic acid
- preparation
- carbon coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000007770 graphite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 150000007524 organic acids Chemical class 0.000 claims abstract description 60
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 50
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 30
- 239000010439 graphite Substances 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 claims abstract description 23
- -1 modified graphite alkene Chemical class 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 13
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- BVWCFOXBDSMXEP-UHFFFAOYSA-N 1-(5-acetyl-2-methoxyphenyl)-3-methylbutan-1-one Chemical compound COC1=CC=C(C(C)=O)C=C1C(=O)CC(C)C BVWCFOXBDSMXEP-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 239000002153 silicon-carbon composite material Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- 150000007974 melamines Chemical class 0.000 description 8
- 230000004224 protection Effects 0.000 description 8
- 102220043159 rs587780996 Human genes 0.000 description 8
- 238000001073 sample cooling Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 235000015165 citric acid Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Classifications
-
- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to technical field of lithium ion, are related to a kind of preparation method of nitrogen-doped carbon coated Si composite graphite material, include the following steps：Using melamine as nitrogen source, organic acid is carbon source, and modified graphene is conductive bridge, and melamine, organic acid, modified graphene are uniformly mixed with nano-silicon suspension, then add graphite, is uniformly mixed, dry；The dried material mixed is ground up, sieved, is then transferred the material into rotary furnace, inert atmosphere is passed through, is heated to 100 ~ 500 DEG C, silicon nanoparticle be embedded in melamine in generated in-situ functional structure component after organic acid, modified graphite alkene reaction；Then proceed to heating carbonization.Compared with the existing technology, the present invention uses situ Nitrogen Doping carbon coating silicon composite graphite material, and to obtain Si-C composite material, the cycle performance of the material promotes apparent, good rate capability.And this method is simple, and it is at low cost, it is very suitable for large-scale production and uses.
Description
Technical field
The invention belongs to technical field of lithium ion, are related to a kind of preparation of nitrogen-doped carbon coated Si composite graphite material
Method.
Background technology
In recent years, due to the continuous development in electric vehicle field, four ministries and commissions such as Ministry of Industry and Information exist at present《Promote automobile power electricity
Pond industry development action scheme》Middle proposition requires single battery energy density to reach 300wh/kg in the year two thousand twenty object of planning, this
For as the conventional lithium ion battery of cathode being a huge challenge using graphite (theoretical gram volume 372mAh/g).And silicon
Theoretical capacity with 4200mAh/g, and low (the ＜ 0.5V Vs Li/Li of deintercalation platform+), silica-base material is to be expected to become next
The material of one of mainstream for ion cathode material lithium.However there are one fatal disadvantages for silica-base material：In lithium ion from silicon material
During expecting deintercalation, volume change is very big, easily leads to the dusting of electrode material and the deterioration of electrode performance, so that battery follows
Ring performance is poor.
In view of this, the present invention is intended to provide a kind of preparation method of nitrogen-doped carbon coated Si composite graphite material, is adopted
With situ Nitrogen Doping carbon coating silicon composite graphite material, to obtain Si-C composite material, the cycle performance promotion of the material is bright
It is aobvious, good rate capability.And this method is simple, and it is at low cost, it is very suitable for large-scale production and uses.
Invention content
It is an object of the invention to：In view of the deficiencies of the prior art, a kind of nitrogen-doped carbon coated Si composite graphite is provided
The preparation method of material uses situ Nitrogen Doping carbon coating silicon composite graphite material, to obtain Si-C composite material, the material
The cycle performance of material promotes apparent, good rate capability.And this method is simple, and it is at low cost, it is very suitable for large-scale production and uses.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material includes at least following steps：
Step 1, using, as nitrogen source, organic acid is carbon source, and modified graphene is conducting bridge with the high melamine of nitrogen content
Melamine, organic acid, modified graphene are uniformly mixed by beam with nano-silicon suspension, then add graphite, and mixing is equal
It is even, it is dry；
The dried material mixed in step 1 is ground up, sieved, then transfers the material into rotary furnace by step 2, leads to
Enter inert atmosphere, be heated to 100~500 DEG C, keep the temperature 0.1~5h, the amino of melamine respectively with organic acid, modified graphene
In carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid
Point.After silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component；So
After be continuously heating to 500~1000 DEG C, the oxygen and hydrogen in functional structure are sloughed in functional structure component carbonization 0.5~for 24 hours, cooling
After break up, be sieved, obtain fine and close nitrogen-doped carbon coated Si composite graphite material.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, what step 2 obtained
Nitrogen-doped carbon coated Si composite graphite material has nucleocapsid, and shell is the N doping carbon-coating for being embedded with nano-silicon, and stratum nucleare is
Graphite, the N doping carbon-coating are by generated in-situ functional structure group after melamine and organic acid, modified graphite alkene reaction
Carbonization is divided to obtain.The shell thickness is in 500nm~5 μm, good conductivity, and, package effect good in graphite surface spreading property
Fruit is excellent, and in addition graphene is flexible, provides space for silicon electrochemical expansion, maintains material structure stability.Function knot
Structure component is uniformly coated on graphite surface.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, the quality of shell are
The 5~30% of stratum nucleare quality.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, described in step 1
Modified graphene is to be grafted with-OOH, and the graphene of-OH functional groups, modified graphene can be anti-with organic acid and melamine
It answers.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, described in step 1
Organic acid is the organic matter containing-COOH, so as to be reacted with melamine and modified graphene heating, systematic function structure group
Point.And the number of-COOH functional groups is 1~5, and carbon atom number is 2~20.Preferably, organic acid be citric acid, stearic acid,
At least one of ethanedioic acid.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, described in step 1
Silicone content in nano-silicon suspension is 5~50%, and the grain size of silicon is 30~100nm, the liquid in nano-silicon suspension be water,
At least one of ethyl alcohol, acetone, isopropanol, n-butanol, tetrahydrofuran and espeleton.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, stone described in step 1
Ink is at least one of artificial graphite, natural graphite and carbonaceous mesophase spherules.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention, described in step 1
60~200 DEG C of dry temperature.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention in step 1, has
Machine acid, modified graphene, melamine, silicon nanoparticle, graphite mass ratio be (10~30)：(0.1~1)：(10~30)：
(0.1~5)：100.
A kind of improvement of preparation method as nitrogen-doped carbon coated Si composite graphite material of the present invention is returned described in step 2
The rotating speed of converter is 0.1rpm~1000rpm；The inert atmosphere includes at least one in helium, nitrogen, argon gas, carbon dioxide
Kind.
Compared with the existing technology, it is to be embedded with the nitrogen of nano-silicon to mix that the material that prepared by the present invention, which has nucleocapsid, shell,
Miscellaneous carbon-coating, stratum nucleare are graphite, wherein N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction
At functional structure component be carbonized.The N-C functional groups that melamine, organic acid and modified graphene reaction in-situ generate
Divide the shell that carbonization obtains conductive good, in the good advantage of graphite surface spreadability, and the flexibility of graphene can give
Silicon expand reserved space, to the present invention material circulation performance and high rate performance it is excellent, can better meet power lithium from
The demand of sub- battery.In addition, present invention process is simple, and it is easy to operate, it is suitable for large-scale production and prepares.
Specific implementation mode
Embodiment 1
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least
Suddenly：
Step 1, weighs 150g melamines first, and 200g citric acids are as organic acid, 5g modified graphene powder,
Silicon suspension (ethanol as solvent) 100g of 10% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, is stirred small-sized
Mixing on device is mixed, 1000g D50=15 μm artificial graphites is then weighed again, pours into agitator tank, after stirring evenly, transfer is put into
It is dry in 80 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is
800rpm is passed through N2 protections, is heated to 300 DEG C, keeps the temperature 3h, the amino of melamine respectively in organic acid, modified graphene
Carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid
Point, after silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.So
After be continuously heating to 800 DEG C carbonization 4h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, are obtained fine and close nitrogen and are mixed
The Si-C composite material of miscellaneous carbon coating silicon composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell,
N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction
At functional structure component be carbonized.The quality of shell is the 15% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 2
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least
Suddenly：
Step 1, weighs 250g melamines first, and 250g citric acids are as organic acid, 8g modified graphene powder,
Silicon suspension (acetone as solvent) 80g of 12% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, is stirred small-sized
Mixing on device is mixed, 1000g D50=10 μm natural graphites is then weighed again, pours into agitator tank, after stirring evenly, transfer is put into
It is dry in 100 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is
600rpm is passed through argon gas protection, is heated to 400 DEG C, keeps the temperature 4h, the amino of melamine respectively with organic acid, modified graphene
In carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid
Point, after silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.So
After be continuously heating to 900 DEG C carbonization 5h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, are obtained fine and close nitrogen and are mixed
The Si-C composite material of miscellaneous carbon coating silicon composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell,
N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction
At functional structure component be carbonized.The quality of shell is the 17% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 3
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least
Suddenly：
Step 1, weighs 200g melamines first, and 180g stearic acid is as organic acid, 4g modified graphene powder,
Silicon suspension (isopropanol makees solvent) 50g of 20% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, small-sized
Then mixing on blender weighs 1000g D50=18 μm natural graphites, pours into agitator tank again, after stirring evenly, transfer is put
Enter dry in 150 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups.
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is
500rpm is passed through argon gas protection, is heated to 200 DEG C, keeps the temperature 2h, the amino of melamine respectively with organic acid, modified graphene
In carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid
Point, after silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.So
After be continuously heating to 700 DEG C carbonization 6h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, are obtained fine and close nitrogen and are mixed
The Si-C composite material of miscellaneous carbon coating silicon composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell,
N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction
At functional structure component be carbonized.The quality of shell is the 18% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 4
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least
Suddenly：
Step 1, weighs 120g melamines first, and 220g ethanedioic acids are as organic acid, 7g modified graphene powder,
Silicon suspension (isopropanol makees solvent) 100g of 25% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, small-sized
Then mixing on blender weighs 1000g D50=20 μm carbonaceous mesophase spherules, pours into agitator tank again, after stirring evenly, turn
Shifting is put into 120 DEG C of baking ovens dry.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups.
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is
300rpm is passed through argon gas protection, is heated to 250 DEG C, keeps the temperature 2.5h, the amino of melamine respectively with organic acid, modified graphite
Carboxyl reaction in alkene, generates key containing C-N, and the hydroxyl in the carboxyl and modified graphene of organic acid generates the functional structure of esters
Component, silicon nanoparticle are embedded in after melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.
It then proceedes to be warming up to 750 DEG C of carbonization 10h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain densification
The Si-C composite material of nitrogen-doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell,
N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction
At functional structure component be carbonized.The quality of shell is the 20% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 5
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least
Suddenly：
Step 1, weighs 280g melamines first, and 110g citric acids are as organic acid, 8g modified graphene powder,
Silicon suspension (ethanol as solvent) 90g of 16% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, is stirred small-sized
Mixing on device is mixed, 1000g D50=15 μm artificial graphites is then weighed again, pours into agitator tank, after stirring evenly, transfer is put into
It is dry in 130 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is
750rpm is passed through N2 protections, is heated to 350 DEG C, keeps the temperature 3.5h, the amino of melamine respectively with organic acid, modified graphene
In carboxyl reaction, generate key containing C-N, the functional structure group of the hydroxyl generation esters in the carboxyl and modified graphene of organic acid
Point, after silicon nanoparticle insertion melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.So
After be continuously heating to 850 DEG C carbonization 12h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain fine and close nitrogen
The Si-C composite material of doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell,
N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction
At functional structure component be carbonized.The quality of shell is the 12% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 6
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least
Suddenly：
Step 1, weighs 260g melamines first, and 130g citric acids are as organic acid, 5.5g modified graphene powder,
Silicon suspension (water as solvent) 70g of 26% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, in small-sized stirring
Then mixing on device weighs 1000g D50=35 μm artificial graphites, pours into agitator tank again, after stirring evenly, transfer is put into
It is dry in 140 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is
550rpm is passed through argon gas protection, is heated to 150 DEG C, keeps the temperature 1.5h, the amino of melamine respectively with organic acid, modified graphite
Carboxyl reaction in alkene, generates key containing C-N, and the hydroxyl in the carboxyl and modified graphene of organic acid generates the functional structure of esters
Component, silicon nanoparticle are embedded in after melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.
It then proceedes to be warming up to 650 DEG C of carbonization 20h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain densification
The Si-C composite material of nitrogen-doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell,
N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction
At functional structure component be carbonized.The quality of shell is the 10% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 7
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least
Suddenly：
Step 1, weighs 160g melamines first, and 230g citric acids are as organic acid, 4.5g modified graphene powder,
Silicon suspension (water as solvent) 75g of 21% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, in small-sized stirring
Then mixing on device weighs 1000g D50=35 μm artificial graphites, pours into agitator tank again, after stirring evenly, transfer is put into
It is dry in 180 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is
650rpm is passed through argon gas protection, is heated to 210 DEG C, keeps the temperature 1.8h, the amino of melamine respectively with organic acid, modified graphite
Carboxyl reaction in alkene, generates key containing C-N, and the hydroxyl in the carboxyl and modified graphene of organic acid generates the functional structure of esters
Component, silicon nanoparticle are embedded in after melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.
It then proceedes to be warming up to 720 DEG C of carbonization 18h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain densification
The Si-C composite material of nitrogen-doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell,
N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction
At functional structure component be carbonized.The quality of shell is the 15% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Embodiment 8
A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material is present embodiments provided, following step is included at least
Suddenly：
Step 1, weighs 155g melamines first, and 205g citric acids are as organic acid, 2.5g modified graphene powder,
Silicon suspension (ethanol as solvent) 80g of 12% solid content is put into agitator tank, and the grain size of silicon is 30~100nm, is stirred small-sized
Mixing on device is mixed, 1000g D50=15 μm artificial graphites is then weighed again, pours into agitator tank, after stirring evenly, transfer is put into
It is dry in 160 DEG C of baking ovens.Wherein, modified graphene is to be grafted with-OOH, the graphene of-OH functional groups
Step 2 is ground after drying, crosses 325 mesh sieve, and powder turns to be put into revolution furnace cavity, and the rotating speed of rotary furnace is
750rpm is passed through argon gas protection, is heated to 230 DEG C, keeps the temperature 1.6h, the amino of melamine respectively with organic acid, modified graphite
Carboxyl reaction in alkene, generates key containing C-N, and the hydroxyl in the carboxyl and modified graphene of organic acid generates the functional structure of esters
Component, silicon nanoparticle are embedded in after melamine and organic acid, modified graphite alkene reaction in generated in-situ functional structure component.
It then proceedes to be warming up to 780 DEG C of carbonization 14h.After sample cooling, sample is taken out, 325 mesh screens are crossed in grinding, obtain densification
The Si-C composite material of nitrogen-doped carbon coated Si composite graphite.
It is to be embedded with nano-silicon that the nitrogen-doped carbon coated Si composite graphite material that step 2 obtains, which has nucleocapsid, shell,
N doping carbon-coating, stratum nucleare is graphite, and N doping carbon-coating is by being given birth in situ after melamine and organic acid, modified graphite alkene reaction
At functional structure component be carbonized.The quality of shell is the 15% of stratum nucleare quality, and shell thickness is in 500nm~5 μm.
Comparative example 1
Using commercially available silicon-carbon cathode, shell is carbon, and stratum nucleare is silicon, and the quality of shell is the 10% of stratum nucleare quality, and shell is thick
Degree is in 500nm~5 μm.
Electrochemistry cycle performance is tested using following methods：The material that material and comparative example 1 prepared by Example 1-8 provides
Material, by following proportioning：Si-C composite material：SP:CMC：SBR=94：2：1.5:2.5 mass ratio mixing, is added suitable pure
Water purification is tuned into slurry as dispersant, is coated on copper foil, and vacuum dried, roll-in, is prepared into negative plate；Anode is using gold
Belong to lithium piece, uses the LiPF of 1mol/L6Three component mixed solvents press the electrolyte of EC: DMC: EMC=1: 1: 1 (v/v) mixing, adopt
It is diaphragm with microporous polypropylene membrane, in the inert atmosphere glove box system assembles full of argon gas at CR2016 type button cells.Button
The charge-discharge test of formula battery is on Shenzhen Xin Wei Co., Ltds Neware battery test systems, in normal temperature condition, 0.1C constant currents
Charge and discharge, charging/discharging voltage are limited in 0.005~1.5V.
Sample prepared by each embodiment and comparative example is assembled into button cell respectively, then carries out electric performance test, for the first time
Charge and discharge gram volume and coulombic efficiency is as described in Table 1 for the first time.
Table 1：Including the button cell for the material that the material and comparative example 1 that are prepared using the method for embodiment 1 to 8 are provided
Electricity
The performance test results.
Table 2：Using the high rate performance test result of embodiment 1 and the button cell of the material of the offer of comparative example 1.
Known to table 1,2：Material circulation performance and high rate performance prepared by method using the present invention is excellent, can be more preferable
Meet the needs of power lithium-ion battery.In addition, present invention process is simple, and it is easy to operate, it is suitable for large-scale production and makes
It is standby.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the invention is not limited in specific implementation modes disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In used some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of preparation method of nitrogen-doped carbon coated Si composite graphite material, which is characterized in that include at least following steps：
Step 1, using melamine as nitrogen source, organic acid is carbon source, and modified graphene is conductive bridge, by melamine, organic
Acid, modified graphene are uniformly mixed with nano-silicon suspension, then add graphite, are uniformly mixed, dry；
The dried material mixed in step 1 is ground up, sieved, then transfers the material into rotary furnace by step 2, is passed through lazy
Property atmosphere, be heated to 100 ~ 500 DEG C, keep the temperature 0.1 ~ 5h, silicon nanoparticle is embedded in melamine and organic acid, modified graphene are anti-
After answering in generated in-situ functional structure component；Then proceed to be warming up to 500 ~ 1000 DEG C, carbonization 0.5 ~ for 24 hours, broken up after cooling,
Sieving obtains fine and close nitrogen-doped carbon coated Si composite graphite material.
2. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step
Two obtained nitrogen-doped carbon coated Si composite graphite materials have nucleocapsid, and shell is the nitrogen-doped carbon for being embedded with nano-silicon
Layer, stratum nucleare is graphite, and the N doping carbon-coating is by generated in-situ work(after melamine and organic acid, modified graphite alkene reaction
Energy structural constituent is carbonized.
3. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 2, which is characterized in that shell
Quality be stratum nucleare quality 5 ~ 30%.
4. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step
Modified graphene described in one is to be grafted with-COOH, the graphene of-OH functional groups.
5. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step
Organic acid described in one is the organic matter containing-COOH, and the number of-COOH functional groups is 1 ~ 5, and carbon atom number is 2 ~ 20.
6. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step
The silicone content in nano-silicon suspension described in one is 5 ~ 50%, and the grain size of silicon is 30 ~ 100nm, the liquid in nano-silicon suspension
For at least one of water, ethyl alcohol, acetone, isopropanol, n-butanol, tetrahydrofuran and espeleton.
7. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step
One graphite is at least one of artificial graphite, natural graphite and carbonaceous mesophase spherules.
8. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step
60 ~ 200 DEG C of the temperature of drying described in one.
9. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step
In one, organic acid, modified graphene, melamine, silicon nanoparticle, graphite mass ratio be（10~30）：（0.1~1）：（10~
30）：（0.1~5）：100.
10. the preparation method of nitrogen-doped carbon coated Si composite graphite material according to claim 1, which is characterized in that step
The rotating speed of rapid two rotary furnace is 0.1rpm ~ 1000rpm；The inert atmosphere includes helium, nitrogen, argon gas, carbon dioxide
At least one of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810592149.1A CN108682829B (en) | 2018-06-11 | 2018-06-11 | Preparation method of nitrogen-doped carbon-coated silicon composite graphite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810592149.1A CN108682829B (en) | 2018-06-11 | 2018-06-11 | Preparation method of nitrogen-doped carbon-coated silicon composite graphite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108682829A true CN108682829A (en) | 2018-10-19 |
| CN108682829B CN108682829B (en) | 2020-10-23 |
Family
ID=63810660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810592149.1A Active CN108682829B (en) | 2018-06-11 | 2018-06-11 | Preparation method of nitrogen-doped carbon-coated silicon composite graphite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108682829B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022142582A1 (en) * | 2020-12-31 | 2022-07-07 | 广东邦普循环科技有限公司 | Silicon-doped graphene composite material, preparation method for same, and applications thereof |
| CN114927678A (en) * | 2022-06-20 | 2022-08-19 | 南昌大学 | A kind of surface modification method of silicon anode material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008186732A (en) * | 2007-01-30 | 2008-08-14 | Nippon Carbon Co Ltd | Negative electrode active material for lithium secondary battery, negative electrode using the same, and manufacturing method |
| CN102214817A (en) * | 2010-04-09 | 2011-10-12 | 清华大学 | Carbon/silicon/carbon nano composite structure cathode material and preparation method thereof |
| CN104143629A (en) * | 2014-08-06 | 2014-11-12 | 广东省工业技术研究院(广州有色金属研究院) | Method for preparing Si/C/graphite composite negative electrode material |
| CN105609730A (en) * | 2016-01-05 | 2016-05-25 | 广州有色金属研究院 | Preparation method for silicon/carbon/graphite composite negative electrode material |
| CN107403919A (en) * | 2017-07-29 | 2017-11-28 | 合肥国轩高科动力能源有限公司 | Composite material of nitrogen-doped carbon material coated with silicon monoxide and preparation method thereof |
| CN108063221A (en) * | 2017-05-11 | 2018-05-22 | 华为技术有限公司 | Prepare method, negative material, cathode pole piece and the lithium ion battery of negative material |
-
2018
- 2018-06-11 CN CN201810592149.1A patent/CN108682829B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008186732A (en) * | 2007-01-30 | 2008-08-14 | Nippon Carbon Co Ltd | Negative electrode active material for lithium secondary battery, negative electrode using the same, and manufacturing method |
| CN102214817A (en) * | 2010-04-09 | 2011-10-12 | 清华大学 | Carbon/silicon/carbon nano composite structure cathode material and preparation method thereof |
| CN104143629A (en) * | 2014-08-06 | 2014-11-12 | 广东省工业技术研究院(广州有色金属研究院) | Method for preparing Si/C/graphite composite negative electrode material |
| CN105609730A (en) * | 2016-01-05 | 2016-05-25 | 广州有色金属研究院 | Preparation method for silicon/carbon/graphite composite negative electrode material |
| CN108063221A (en) * | 2017-05-11 | 2018-05-22 | 华为技术有限公司 | Prepare method, negative material, cathode pole piece and the lithium ion battery of negative material |
| CN107403919A (en) * | 2017-07-29 | 2017-11-28 | 合肥国轩高科动力能源有限公司 | Composite material of nitrogen-doped carbon material coated with silicon monoxide and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022142582A1 (en) * | 2020-12-31 | 2022-07-07 | 广东邦普循环科技有限公司 | Silicon-doped graphene composite material, preparation method for same, and applications thereof |
| GB2616799A (en) * | 2020-12-31 | 2023-09-20 | Guangdong Brunp Recycling Technology Co Ltd | Silicon-doped graphene composite material, preparation method for same, and applications thereof |
| GB2616799B (en) * | 2020-12-31 | 2025-02-12 | Guangdong Brunp Recycling Technology Co Ltd | Silicon-doped graphene-based composite material, preparation method and application thereof |
| CN114927678A (en) * | 2022-06-20 | 2022-08-19 | 南昌大学 | A kind of surface modification method of silicon anode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108682829B (en) | 2020-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108736007B (en) | Preparation method of high-compaction-density lithium ion battery silicon-carbon negative electrode material | |
| CN106025221B (en) | A kind of preparation method of silicon/carbon graphite composite negative pole material | |
| CN108565446B (en) | Preparation method of porous nitrogen-doped carbon-coated graphite material | |
| CN107634208A (en) | A kind of preparation method of lithium ion battery silicon-carbon cathode material | |
| CN108807896A (en) | A kind of preparation method of nitrogen-doped carbon cladding Si-C composite material | |
| CN108807917B (en) | Nitrogen-sulfur double-doped graphene composite silicon-boron-carbon-nitrogen ceramic composite material, preparation method and application | |
| CN106920954A (en) | A kind of preparation of porous silicon composite cathode material of graphene coated and application process | |
| CN110212162B (en) | A kind of flexible gel sulfur cathode for lithium-sulfur battery and preparation method thereof | |
| CN106450295B (en) | A kind of sodium ion battery positive electrode material Na3Fe2(PO4)3 and preparation method thereof | |
| CN111293308B (en) | A kind of negative electrode material, negative electrode, potassium ion battery and preparation method | |
| CN108899488A (en) | Modified carbon-coated silicon monoxide composite material, preparation method and application thereof | |
| WO2025015813A1 (en) | Silicon-carbon composite material containing carbon nanotubes, and preparation method therefor and use thereof | |
| CN112928246A (en) | Composite material, preparation method and application thereof | |
| CN113292065A (en) | Large-interlayer-spacing monodisperse nano hard carbon material, and synthesis method and application thereof | |
| CN110350175B (en) | Porous carbon @ graphene sulfur-loaded composite material, preparation method and application thereof | |
| CN106654266A (en) | Preparation method of nano-particle/carbon composite material and electrode battery | |
| CN113659120B (en) | Elastic aerogel derived high-capacity silicon oxygen carbon lithium battery negative electrode material and preparation method thereof | |
| CN113479890B (en) | Silicon-based negative electrode material and preparation method and application thereof | |
| CN108682829A (en) | A kind of preparation method of nitrogen-doped carbon coated Si composite graphite material | |
| CN108682828B (en) | Preparation method of nitrogen-doped carbon-coated positive electrode material | |
| CN108695509B (en) | Composite lithium battery positive electrode with high energy storage efficiency, preparation method thereof and lithium battery | |
| Yuan et al. | Facile synthesis of SiO2/C composite and its application as anode material for lithium ion batde | |
| CN112038628A (en) | A layered cobalt-based sodium-ion battery cathode material, preparation method and application thereof | |
| CN108695496B (en) | Graphene-coated porous red phosphorus, conductive carbon composite material, preparation method and application | |
| CN115692652B (en) | Nitrogen-doped carbon nanomaterial, preparation method thereof and application as negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 518000 Tsinghua campus, Xili University Town, Nanshan District, Shenzhen City, Guangdong Province Patentee after: Tsinghua Shenzhen International Graduate School Patentee after: HUBEI RT ADVANCED MATERIALS Co.,Ltd. Address before: 518055 Guangdong city of Shenzhen province Nanshan District Xili of Tsinghua Patentee before: GRADUATE SCHOOL AT SHENZHEN, TSINGHUA University Patentee before: HUBEI RT ADVANCED MATERIALS Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220208 Address after: 435100 No. 66 Changle Avenue, Luojiaqiao Street, Daye City, Huangshi City, Hubei Province Patentee after: HUBEI RT ADVANCED MATERIALS Co.,Ltd. Address before: 518000 Tsinghua campus, Xili University Town, Nanshan District, Shenzhen City, Guangdong Province Patentee before: Tsinghua Shenzhen International Graduate School Patentee before: HUBEI RT ADVANCED MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 435100 No. 66 Changle Avenue, Luojiaqiao Street, Daye City, Huangshi City, Hubei Province Patentee after: Hubei Rongtong High tech Advanced Materials Group Co.,Ltd. Address before: 435100 No. 66 Changle Avenue, Luojiaqiao Street, Daye City, Huangshi City, Hubei Province Patentee before: HUBEI RT ADVANCED MATERIALS Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |