CN108493450A - Carbon material, method for generating carbon material by taking residual oil as raw material, lithium battery negative electrode plate and lithium ion battery - Google Patents
Carbon material, method for generating carbon material by taking residual oil as raw material, lithium battery negative electrode plate and lithium ion battery Download PDFInfo
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- CN108493450A CN108493450A CN201810292377.7A CN201810292377A CN108493450A CN 108493450 A CN108493450 A CN 108493450A CN 201810292377 A CN201810292377 A CN 201810292377A CN 108493450 A CN108493450 A CN 108493450A
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- carbon material
- residual oil
- carbonate
- carbon
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 239000002994 raw material Substances 0.000 title claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 32
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 15
- 239000001110 calcium chloride Substances 0.000 claims description 15
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 56
- 239000000463 material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 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 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- -1 for example Inorganic materials 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241001661355 Synapsis Species 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a carbon material, a method for generating the carbon material by taking residual oil as a raw material, a lithium battery cathode electrode plate and a lithium ion battery, wherein the method comprises the following steps: providing a residuum; mixing residual oil and a carbonate template agent, heating and liquefying, and then carrying out carbonization treatment under an anaerobic condition to form a carbonized product; contacting the carbonized product with a weak acid to form the carbon material. The method has simple process steps and easy operation, and the carbon material prepared by the method has larger specific surface area and better lithium intercalation capability, and can be used for preparing the negative electrode plate of the lithium battery so as to reduce the preparation cost of the electrode plate under the condition of realizing waste utilization of residual oil.
Description
Technical field
The present invention relates to battery raw material manufacturing fields, are generated in particular to a kind of carbon material and by raw material of residual oil
The method and lithium cell negative pole electrode slice and lithium ion battery of carbon material.
Background technology
Residual oil has the characteristics that derive from a wealth of sources, is cheap.The application of existing residual oil is relatively broad, for example, it can be with
Light oil is prepared by technologies such as visbreaking plus hydrogen, coking, catalytic cracking；In another example it can by solvent deasphalting,
The technologies such as coking, high temperature cabonization, CVD deposition prepare pitch, petroleum coke, energy-storage nano carbon material etc..
As carbon material is in the further investigation of energy storage field, the extract again of residual oil is used to prepare energy storage carbon material for carbon source
It is proved to be a kind of feasible approach.When directly nano-carbon material is prepared as carbon source using residual oil when, can simplify it is above-mentioned with
Extract is the step of carbon source prepares energy storage material to residual oil again.The direction is very few in the research of energy storage field so far, has
The bright prospects of further investigation.
Invention content
The object of the present invention is to provide a kind of carbon material and the method for carbon material is generated as raw material using residual oil and lithium electricity is born
Pole electrode slice and lithium ion battery, under relatively simple process flow, to prepare energy storage carbon material.
For this purpose, providing a kind of method generating carbon material as raw material using residual oil in the present invention, this method includes：It provides
Residual oil；The residual oil is mixed with carbonate template, it is heats liquefied, carbonization treatment is then carried out under anaerobic, is formed
Carbonized product；The carbonized product is contacted with acid solution, forms the carbon materials.
Preferably, C content is more than 80wt% in the residual oil, N content is more than 0.15wt%, and S contents are more than
0.3wt%；It is preferred that N content is more than 0.3wt% in the residual oil, S contents are more than 3wt%.
Preferably, the content of saturated hydrocarbons is less than 40wt% in the residual oil, aromatic hydrocarbon content is more than 30wt%.
Preferably, the residual oil is reduced crude or decompression residuum.
Preferably, the carbonate template be one kind in calcium carbonate, magnesium carbonate, barium carbonate and zinc carbonate or
It is several.
Preferably, it is preferred that the carbonate template is calcium carbonate template；
Preferably, the carbonate template is obtained by coprecipitation；
Preferably, the calcium carbonate template is formed with sodium carbonate and calcium chloride co-percipitation；
Preferably, the step of preparing the calcium carbonate template includes：Sodium carbonate is dissolved in water, sodium carbonate is formed
Aqueous solution；Calcium chloride is dissolved in water, calcium chloride water is formed；The aqueous sodium carbonate and the calcium chloride is water-soluble
After liquid mixing, centrifuge washing forms the calcium carbonate template；
Preferably, the weight ratio of the sodium carbonate and carbonate template is (0.8-1.2)：1.
Preferably, the residual oil based on 100 parts by weight, the dosage of the carbonate template is 26.5-120 weight
Part, preferably 30-100 parts by weight.
Preferably, the step of heats liquefied residual oil, includes：Under the conditions of oil bath, heating is heated to 110 DEG C -150
DEG C, keep 20min-40min.
Preferably, the step of carbonization treatment is to carry out under an inert atmosphere, the preferably described inert atmosphere is to pass through
It is passed through argon gas to be formed, the intake of the argon gas is 50mL/min-200mL/min；
Preferably, the step of carbonization treatment, includes：Under an inert atmosphere, 300 DEG C -600 DEG C are warming up to, when holding
Between be 30min-90min, then rise to 800 DEG C -900 DEG C, retention time 30min-90min.
Preferably, the condition that the carbonized product is contacted with acid solution includes：At 10 DEG C -40 DEG C, contact treatment 60-
120min。
Preferably, the acid solution is selected from one or more of acetic acid, oxalic acid and phosphoric acid.
Meanwhile a kind of carbon material is additionally provided in the present invention, the carbon material is according to of the present invention with residual oil
The method for generating carbon material for raw material is prepared.
Meanwhile a kind of carbon material is additionally provided in the present invention, which is porous particle object, and wherein doped with N
And S.
Preferably, the granularity of the carbon material is 300nm-800nm, a diameter of 10- of carbon material Hole
The specific surface area of 100nm, the carbon material are 600m2/g-900m2/g。
Preferably, the doping of N is 0.15-0.6wt% in the carbon material, the doping of S is 0.3-6wt%.
Meanwhile a kind of lithium cell negative pole electrode slice, including conductive agent, binder and carbon material are provided in the present invention, it should
Carbon material includes carbon material according to the present invention；
Preferably, with weight, the carbon material is the 60-80wt% of conductive agent.
Preferably, the conductive agent further includes acetylene black, expanded graphite, Ketjen black, carbon nanotube conducting slurry and surpasses
Lead at least one of carbon black.
In addition, a kind of lithium ion battery is additionally provided in the present invention, including cathode, anode, battery diaphragm and electrolysis
Liquid, the cathode include lithium cell negative pole electrode slice according to the present invention.
Using carbon material of the present invention and using residual oil as the method for raw material generation carbon material and lithium cell negative pole electrode slice and lithium
Ion battery, the carbon materials obtained by being mixed with residual oil with carbonate template, then by hot melt, carbonization treatment；
This method processing step is simple, easy to operate, and bottoms conversion is high, and carbon materials specific surface area prepared by this method
It is larger, there is preferable conductive effect, can be used for preparing electrode slice, in the case where realizing waste utilization to residual oil, to reduce
The manufacturing cost of electrode slice.
Specific implementation mode
With reference to specific embodiment, present invention is further described in detail, but not as a limitation of the invention.
In order to find a kind of simple residual oil reuse method of processing step, provide one kind in the present invention is with residual oil
The method that raw material generates carbon material, this method include：Residual oil is provided；The residual oil is mixed with carbonate template, heats liquid
Change, then carries out carbonization treatment under anaerobic, the carbonized product is contacted with acid solution, form the carbon material.
In the present invention, used carbonate template raw material is cheap, is readily synthesized, and under the acidification of acid solution
It can react, become gas, gas contributes to increase the specific surface area of carbon material in generating process, forms micropore, into
And form the suitable carbon material of specific surface area.
According to the method for the present invention, can there is no particular/special requirement for residual oil, however, for the conduction effect of preferred carbon materials
Fruit, under preferable case, C content is more than 80wt% in the residual oil, and N content is more than 0.15wt%, and S contents are more than 0.3wt%；It is excellent
N content in the residual oil is selected to be more than 0.3wt%, S contents are more than 3wt%；It is preferred that the content of saturated hydrocarbons is less than in the residual oil
40wt%, aromatic hydrocarbon content are more than 30wt%；It is preferred that the residual oil is reduced crude or decompression residuum.It is of the present invention
The ingredient of above-mentioned residual oil may be used using gas chromatograph (GC), such as instrument model is that Agilent 7890A tests obtain,
It is equipped with 13x molecular sieve columns during the test, it is another to use nonpolarity chromatographic column DB-1 and damping column.
According to the method for the present invention, wherein can not have particular/special requirement for carbonate template, commercially available production may be used
Product, such as selected from one or more of calcium carbonate, magnesium carbonate, barium carbonate and zinc carbonate, the preferably described carbonate template is
Calcium carbonate template.In order to optimize the electric conductivity of prepared carbon material, under preferable case, the calcium carbonate template passes through
Coprecipitation obtains；Such as the calcium carbonate template is formed with sodium carbonate and calcium chloride co-percipitation；A kind of relatively specific
Embodiment in, the step of preparing the calcium carbonate template includes：Sodium carbonate is dissolved in water, it is water-soluble to form sodium carbonate
Liquid；Calcium chloride is dissolved in water, calcium chloride water is formed；The aqueous sodium carbonate and the calcium chloride water are mixed
After conjunction, centrifuge washing forms the calcium carbonate template.Under preferable case, the weight ratio of the sodium carbonate and calcium chloride is
(0.8-1.2)：1.
According to the method for the present invention, the dosage of the carbonate template mixed with residual oil can not required, however,
In order to preferably residual oil be promoted to be modified, under preferable case, the residual oil based on 100 parts by weight, the carbonate template
Dosage is 26.5-120 parts by weight.
It according to the method for the present invention,, can during heats liquefied residual oil after mixing residual oil with carbonate template
With no particular/special requirement, as long as reasonably control temperature.Under preferable case, the step of heats liquefied residual oil, includes：
Under the conditions of oil bath, heating is heated to 110 DEG C -150 DEG C, keeps 20min-40min.It is heated in the present invention by liquid bath mixed
Residual oil and carbonate template are closed, is conducive to that the two is promoted to be uniformly mixed.In view of residual oil by sticky state become the temperature of liquid compared with
Height is unsuitable for using waters, it is preferred to use oil bath, the wherein material of oil bath can be lubricating oil or silicone oil.
According to the method for the present invention, after the step of completing heats liquefied residual oil, the step of carbonization treatment is carried out to mixture
Suddenly the technique that conventional carbonization treatment may be used, such as under an inert atmosphere, be warming up to 300 DEG C -600 DEG C, retention time be
30min-90min then rises to 800 DEG C -900 DEG C, retention time 30min-90min.In the carbonization treatment the step of, pass through
Using inert atmosphere, is conducive to completely cut off air, prevents carbon oxidation by air during high temperature cabonization from becoming carbon dioxide.
Wherein, under preferable case, the inert atmosphere is formed by being passed through argon gas, and the intake of the argon gas is
50mL/min-200mL/min。
Wherein, under preferable case, 300 DEG C -600 is risen to the rate of 3 DEG C/min-6 DEG C/min during carbonization treatment
DEG C, 800 DEG C -900 DEG C then are risen to the rate of 3 DEG C/min-6 DEG C/min, retention time 30min-90min.Pass through control
The intake of heating rate and argon gas in the range, can ensure that multistage carbon material can obtain preferable degree of graphitization,
Material specific surface area is big, and then is suitable as lithium cell negative pole material.
According to the method for the present invention, wherein the acid solution contacted with carbonized product is one in acetic acid, oxalic acid and phosphoric acid
Kind is several；It is preferred that a concentration of 0.5mol/L- of a concentration of 1mol/L-5mol/L of the acetic acid, the oxalic acid and phosphoric acid
3mol/L。
According to the method for the present invention, the condition that the carbonized product is contacted with weak acid includes：At 300 DEG C -600 DEG C, connect
Synapsis manages 30-90min.
A kind of carbon material is additionally provided in the present invention, which is to be given birth to by raw material of residual oil according to of the present invention
It is prepared at the method for carbon material.
The carbon material provided in the present invention is porous particle object, and due to being original with residual oil (wherein containing N and S)
Material so that also doped with N and S in prepared carbon material, this allow for this carbon material prepared by the present invention with it is existing
There are larger differences for conventional carbon, and then are conducive to improve the embedding lithium ability of the carbon material.Under preferable case, the carbon materials
The doping of N is 0.15-0.6wt% in material, and the doping of S is 0.3-6wt%.In the case of furthermore it is preferred that, the grain of the carbon materials
Degree is 300nm-800nm, and the specific surface area of a diameter of 10-100nm of carbon materials Hole, the carbon materials are 600m2/g-
900m2/g。
Meanwhile a kind of lithium cell negative pole electrode slice, including conductive agent and binder, the conduction are additionally provided in the present invention
Agent includes carbon materials according to the present invention；
Under preferable case, with weight, the carbon materials are the 60-80wt% of conductive agent.
Under preferable case, the conductive agent further include acetylene black, expanded graphite, Ketjen black, carbon nanotube conducting slurry and
At least one of superconduction carbon black.
Under preferable case, the binder is Kynoar (PVDF), aqueous sodium alginate or carboxymethyl cellulose
Sodium (CMC)+butadiene-styrene rubber (SBR).
The weight ratio of conductive agent and binder is 1-3 in the electrode slice：1.
In addition, a kind of lithium ion battery is additionally provided in the present invention, including cathode, anode, battery diaphragm and electrolysis
Liquid, the cathode include electrode slice according to the present invention.
The positive plate is to be coated on aluminium by being tuned into slurry for the positive electrode, conductive agent and binder of lithium ion battery
It is made on foil.Positive electrode used includes the positive electrode that arbitrarily can be used for lithium ion battery, for example, cobalt acid lithium, nickel cobalt manganese
Sour lithium, LiMn2O4, LiFePO 4 (LiFePO4At least one of) etc..
The electrolyte is known to the skilled person, and is usually made of electrolyte lithium salts and organic solvent.Wherein,
Electrolyte lithium salts uses dissociable lithium salts, for example, lithium hexafluoro phosphate (LiPF can be selected from6), lithium perchlorate (LiClO4), four
Lithium fluoroborate (LiBF4) etc. at least one of, organic solvent can be selected from ethylene carbonate (EC), propene carbonate (PC),
At least one in dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC), vinylene carbonate (VC) etc.
Kind.Preferably, in the electrolyte electrolyte lithium salts a concentration of 0.8-1.5mol/L.
The battery diaphragm of this field routine may be used in the battery diaphragm, for example, commercially available from Celgard companies
Celgard2300
Lithium ion battery provided by the invention it is main the improvement is that provide a kind of carbon materials are prepared using residual oil
Method, and the carbon materials prepared in this way are further prepared for electrode slice and positive plate, negative plate, battery diaphragm and electrolyte
Arrangement mode (connection type) can be same as the prior art, can know to this those skilled in the art, therefore not to repeat here.
Lithium ion battery provided by the invention has many advantages, such as that good cycle, capacity are high, coulombic efficiency is high for the first time.
The preparation method of lithium ion battery provided by the invention includes stacking gradually positive plate, battery diaphragm and negative plate
Or be wound into pole piece, then inject and electrolyte and seal into the pole piece, wherein the battery diaphragm be above-mentioned battery every
Film.
The advantageous effect further illustrated the present invention below with reference to specific implementation mode.
Residual oil ingredient employed in following example is as shown in table 1.
Table 1.
The ingredient of above-mentioned residual oil is by gas chromatograph (GC), and instrument model is that Agilent7890A tests obtain.
Embodiment 1
(1) multistage carbon material is prepared：1g Kuwait decompression residuum is weighed first in beaker, forms A；Weigh 1.06g
NaCO3It is dissolved in 100mL water, stirs 30min, form B solution；It weighs 1.11g calcium chloride to be dissolved in 100mL water, it is molten to form C
Liquid；B is instilled in C after being co-precipitated, centrifuge washing 3 times obtains D；D is poured into A, it is same to evaporate water by 110 DEG C of heating 2h of oil bath (silicone oil)
When dissolve residual oil, obtain E；Then, E is transferred on magnetic boat, with 3 DEG C/min in the Ar atmosphere that gas flow rate is 100mL/min
Heating rate rise to 300 DEG C, keep 1h, then 800 DEG C are risen to 3 DEG C/min, keep 1h, obtain carbonized product；Finally, by carbon
Change product and be added to prepared 1mol/L acetums 50mL, after stirring 30min, filtering and washing drying obtains final more
Grade carbon material；Prepared carbon materials are porous particle object after tested, and the doping of N is 0.34wt% in the carbon material, and S's mixes
Miscellaneous amount is 4.9wt%；The average particle size of the carbon material is 600nm, a diameter of 10-100nm of carbon materials Hole, the carbon
The specific surface area of material is 836m2/g。
(2) electrode slice is prepared：By aforementioned multistage carbon materials with acetylene black, PVDF by weight 8：1：1, it weighs to be placed on and grind
In Portland, NMP formation slurry appropriate is added dropwise after grinding 2h, then slurry is applied on copper foil, then by obtained pole piece at 80 DEG C
Above-mentioned pole piece is fabricated to circular electric pole piece (radius 0.5cm) by lower dry 3h using punching machine equipment as decompressor, note of weighing
Record active matter quality is 1.364mg.
(3) lithium ion battery is prepared：Then above-mentioned pole piece is transferred in the glove box full of high-purity Ar, it is suitable according to assembling
Sequence is that (it is 1 that bath composition is by volume ratio to negative electrode casing-lithium piece (half-cell cathode)-diaphragm-immersion BLE-207 types electrolyte:
1:1 DMC+DEC+DC and a concentration of 1mol/L LiPF6Composition)-positive plate (former electrodes piece), it is assembled into button half-cell.
Half-cell is stood again and carries out charge discharge test afterwards for 24 hours.
Embodiment 2
(1) multistage carbon material is prepared：2g Kuwait decompression residuum is weighed in beaker, forms A；Weigh 1.06g NaCO3
It is dissolved in 50mL water, stirs 20min, form B solution；It weighs 1.11g calcium chloride to be dissolved in 50mL water, forms C solution；By B drops
Enter, centrifuge washing 3 times obtains D；D is poured into A, 120 DEG C of heat treatment 1h of oil bath (silicone oil), liquefy residual oil while evaporating water, obtains
E；Then E will be set to be transferred on magnetic boat, in the Ar atmosphere that gas flow rate is 200mL/min, with the heating rate liter of 5 DEG C/min
To 500 DEG C, 0.5h is kept, then 900 DEG C are risen to 5 DEG C/min, keep 1h, obtain carbonized product；Finally, carbonized product is added
To the 5mol/L acetum 50mL configured, after stirring 10min, filtering and washing drying obtains final multistage carbon material；Through
Prepared carbon material is tested as porous particle object, the doping of N is 0.18wt% in the carbon material, and the doping of S is
0.33wt%；The average particle size of the carbon material is 500nm, a diameter of 30-90nm of carbon material Hole, the carbon material
Specific surface area be 758m2/g。
(2) electrode slice is prepared：Using method in embodiment 1, difference lies in replace embodiment 1 using aforementioned multistage carbon material
In multistage carbon material.
(3) lithium ion battery is prepared：Using method in embodiment 1, difference lies in replace embodiment 1 using former electrodes piece
In positive plate.
Embodiment 3
(1) multistage carbon material is prepared：It is grand celebration normal pressure slag difference lies in used residual oil using method in embodiment 1
Oil.Prepared carbon material is porous particle object after tested, and the doping of N is 0.36wt%, the doping of S in the carbon material
For 3.1wt%；The average particle size of the carbon material is 700nm, a diameter of 50-100nm of carbon material Hole, the carbon materials
The specific surface area of material is 674m2/g；
(2) electrode slice is prepared：Using method in embodiment 1, difference lies in replace embodiment 1 using aforementioned multistage carbon material
In multistage carbon material.
(3) lithium ion battery is prepared：Using method in embodiment 1, difference lies in replace embodiment 1 using former electrodes piece
In positive plate.
Embodiment 4
(1) multistage carbon material is prepared：Using method in embodiment 1, difference lies in during obtaining carbonized product, argon
The intake of gas is 20mL/min.Prepared carbon materials are porous particle object after tested, and the doping of N is in the carbon material
The doping of 0.7wt%, S are 6.3wt%；The average particle size of the carbon material is 650nm, and the carbon material Hole is a diameter of
The specific surface area of 110-150nm, the carbon materials are 200m2/g；
(2) electrode slice is prepared：Using method in embodiment 1, difference lies in replace embodiment 1 using aforementioned multistage carbon material
In multistage carbon material.
(3) lithium ion battery is prepared：Using method in embodiment 1, difference lies in replace embodiment 1 using former electrodes piece
In positive plate.
Embodiment 5
(1) multistage carbon materials are prepared：Using method in embodiment 1, difference lies in by carbonized product and acetic acid mixing 10min.
Prepared carbon material is porous particle object after tested, and the doping of N is 0.42wt% in the carbon material, and the doping of S is
2.1wt%；The average particle size of the carbon material is 800nm, a diameter of 130-160nm of carbon material Hole, the carbon materials
The specific surface area of material is 168m2/g；
(2) electrode slice is prepared：Using method in embodiment 1, difference lies in replaced in embodiment 1 using aforementioned multistage carbon materials
Multistage carbon materials
(3) lithium ion battery is prepared：Using method in embodiment 1, difference lies in replace embodiment 1 using former electrodes piece
In cathode.
Test：
Normal-temperature circulating performance：The battery of aforementioned preparation is carried out constant current constant voltage with the electric current of 0.2C respectively to recycle 100 weeks, the
The ratio of 100 weeks discharge capacities and the 1st discharge capacity is 100 weeks normal temperature circulation capacity retention ratios of the battery.
First week specific discharge capacity and first all coulombic efficiencies：By the battery of aforementioned preparation respectively with the electric current of 0.2C, the 1st week puts
Electric specific capacity and all specific discharge capacities headed by the ratio of active material quality, first week specific discharge capacity and first week charging specific volume
All coulombic efficiencies headed by the ratio of amount.
Test result：As shown in table 2.
Table 2.
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Normal temperature circulation conservation rate | 96.5% | 97.2% | 97.2% | 52.3% | 64.1% |
| First week specific discharge capacity | 863mAh/g | 794mAh/g | 891mAh/g | 382mAh/g | 357mAh/g |
| First week coulombic efficiency | 82% | 84.2% | 87.2% | 57.2% | 65.9% |
It can be seen that in the preferred embodiment of the present invention 1-3 relative to embodiment 4-5 have excellent by data in table 2
Normal temperature circulation conservation rate, first all specific discharge capacities and first all coulombic efficiencies, are primarily due in the item for preferably preparing carbon material
Under part, the multistage carbon of preparation increases the capacity of the embedding lithium of carbon material surface, and multistage carbon periphery is by one than more uniform carbon shell
It surrounds, can be promoted to the first effect of material has positive effect.But embodiment 4-5 is not on the optimum condition of our inventions
Under, do not prepare the multistage carbon structure that big carbon shell surrounds, therefore normal temperature circulation conservation rate and first all coulombic efficiencies have it is apparent poor
It is different.
Certainly, it is above the preferred embodiment of the present invention.It should be pointed out that for those skilled in the art
For, under the premise of not departing from general principles, several improvements and modifications can also be made, these improvements and modifications
It is considered as protection scope of the present invention.
Claims (11)
1. a kind of method generating carbon material as raw material using residual oil, which is characterized in that the method includes：
Residual oil is provided；
The residual oil is mixed with carbonate template, it is heats liquefied, carbonization treatment is then carried out under anaerobic, forms carbon
Change product；
The carbonized product is contacted with acid solution, forms the carbon materials.
2. method according to claim 1, which is characterized in that C content is more than 80wt% in the residual oil, and N content is more than
0.15wt%, S content are more than 0.3wt%；It is preferred that N content is more than 0.3wt% in the residual oil, S contents are more than 3wt%；It is preferred that
The content of saturated hydrocarbons is less than 40wt% in the residual oil, and aromatic hydrocarbon content is more than 30wt%；It is preferred that the residual oil is reduced crude
Or decompression residuum.
3. method according to claim 1, which is characterized in that the carbonate template is selected from calcium carbonate, magnesium carbonate, carbon
One or more of sour barium and zinc carbonate；
It is preferred that the carbonate template is calcium carbonate template；
It is preferred that the carbonate template is obtained by coprecipitation；
Preferably, the calcium carbonate template is formed with sodium carbonate and calcium chloride co-percipitation；
Preferably, the step of preparing the calcium carbonate template include：
Sodium carbonate is dissolved in water, aqueous sodium carbonate is formed；
Calcium chloride is dissolved in water, calcium chloride water is formed；
After the aqueous sodium carbonate and the calcium chloride water are mixed, centrifuge washing forms the calcium carbonate template；
Preferably, the weight ratio of the sodium carbonate and carbonate template is (0.8-1.2)：1.
4. method according to claim 1, which is characterized in that the residual oil based on 100 parts by weight, the carbonate template
The dosage of agent is 26.5-120 parts by weight, preferably 30-100 parts by weight.
5. method according to claim 1, which is characterized in that the step of heats liquefied residual oil includes：In oil bath condition
Under, heating is heated to 110 DEG C -150 DEG C, keeps 20-40min.
6. method according to claim 1, which is characterized in that the step of carbonization treatment is to carry out under an inert atmosphere,
It is preferred that the inert atmosphere is formed by being passed through argon gas, the intake of the argon gas is 50mL/min-200mL/min；
Preferably, the step of carbonization treatment includes：Under an inert atmosphere, 300 DEG C -600 DEG C are warming up to, the retention time is
30min-90min then rises to 800 DEG C -900 DEG C, retention time 30min-90min.
7. method according to claim 1, which is characterized in that the condition that the carbonized product is contacted with acid solution includes：10
At DEG C -40 DEG C, contact treatment 60-120min；
Preferably, the acid solution is selected from one or more of acetic acid, oxalic acid and phosphoric acid.
8. a kind of carbon material, which is characterized in that the carbon material is described in any one of claim 1 to 7 is with residual oil
The method that raw material generates carbon material is prepared.
9. a kind of carbon material, which is characterized in that the carbon material is porous particle object, and wherein doped with N and S；
Preferably, the granularity of the carbon material be 300nm-800nm, a diameter of 10-100nm of carbon material Hole, it is described
The specific surface area of carbon material is 600m2/g-900m2/g；
Preferably, the doping of N is 0.15-0.6wt% in the carbon material, and the doping of S is 0.3-6wt%.
10. a kind of lithium cell negative pole electrode slice, including conductive agent, binder and carbon material, which is characterized in that wrapped in the carbon material
Include the carbon material described in claim 8 or 9；
Preferably, with weight, the carbon material is the 60-80wt% of conductive agent.
Preferably, the conductive agent further includes acetylene black, expanded graphite, Ketjen black, carbon nanotube conducting slurry and superconduction carbon black
At least one of.
11. a kind of lithium ion battery, including cathode, anode, battery diaphragm and electrolyte, which is characterized in that the cathode packet
Include lithium cell negative pole electrode slice according to any one of claims 10.
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