CN107919461A - Preparation method and application of nitrogen-doped porous carbon negative electrode material - Google Patents
Preparation method and application of nitrogen-doped porous carbon negative electrode material Download PDFInfo
- Publication number
- CN107919461A CN107919461A CN201610883652.3A CN201610883652A CN107919461A CN 107919461 A CN107919461 A CN 107919461A CN 201610883652 A CN201610883652 A CN 201610883652A CN 107919461 A CN107919461 A CN 107919461A
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- Prior art keywords
- lithium
- nitrogen
- porous carbon
- doping
- carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 title 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010406 cathode material Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003610 charcoal Substances 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
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- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- -1 graphite Alkene Chemical class 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011149 active material Substances 0.000 claims description 5
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
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- 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 claims description 2
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
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- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
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- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 claims description 2
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- MEAHOQPOZNHISZ-UHFFFAOYSA-M cesium;hydrogen sulfate Chemical compound [Cs+].OS([O-])(=O)=O MEAHOQPOZNHISZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
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- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
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- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
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- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
- HPCCWDVOHHFCKM-UHFFFAOYSA-M lithium;hydrogen sulfate Chemical compound [Li+].OS([O-])(=O)=O HPCCWDVOHHFCKM-UHFFFAOYSA-M 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013465 LiC12 Inorganic materials 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- HZKFXVSDNZJPND-UHFFFAOYSA-J dimagnesium disulfate Chemical compound [Mg+2].[Mg+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HZKFXVSDNZJPND-UHFFFAOYSA-J 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of carbon material preparation, and belongs to the field of alkali metal ion secondary energy storage. Relates to a method for preparing nitrogen-doped porous carbon by taking nitrogen-containing polycyclic aromatic hydrocarbons of perinone as a carbon source and application of the nitrogen-doped porous carbon as a cathode or anode material of an alkali metal ion secondary battery. The method comprises the steps of mixing the nitrogen-containing conjugated polycyclic aromatic hydrocarbons of the perinone with a template agent or an activating agent, and carrying out pyrolysis and carbonization at a certain range of temperature to obtain the nitrogen-doped porous carbon cathode or anode material. The nitrogen loss in the heat treatment process can be reduced by taking the large-molecular-weight purple-ring ketone nitrogen-containing conjugated polycyclic aromatic hydrocarbon as a carbon source, high-proportion nitrogen doping in the porous carbon is effectively realized, and electrochemical redox sites are effectively increased. The method can also regulate and control the specific surface area of the porous carbon by screening a carbon source, the heat treatment carbonization temperature, the mass ratio of a template agent or an activating agent and the like, increase a charge exchange interface and effectively realize high-energy storage. The material has: (1) the structure is rich, and the raw materials of the rhodocyclic ketone are cheap and easy to obtain; (2) higher energy density, multiplying power density and cyclic stability.
Description
Technical field
Present invention relates particularly to a kind of preparation method of the porous carbon cathode material of N doping, and it is related to these materials and is preparing
During use the step of and raw material.
Technical background
Electronic information epoch people are growing to portable, high-power, high-intelligentization power-supply device demand so that high
Performance energy-storage system has become energy field research and the common issue applied and urgently realized.Subtract in traditional energy deposit
Less, under global warming, the multiple objective force increasingly strengthened of living environment protection promote, production of energy and occupation mode to
New cleaning fuel is changed.Now, the appearance of efficient secondary energy storage device and key technology and material is electronic information intelligence
Change the preference that equipment provides convenient energy source and power support, and weight in energy project is classified as by China and numerous international bodies
One of high-performance energy storage technology that point is supported.Wherein, nineteen ninety by the brand-new lithium of Sony corporation of Japan large-scale commercial from
Sub- secondary cell (also known as lithium ion battery, lithium ion battery), due to operating voltage height, high power capacity, application
Temperature range is wide, self-discharge rate is low, has extended cycle life, has a safety feature and the excellent comprehensive performances such as environmental pollution is light,
Portable, intelligent electronic equipment field is just widely studied, development and application, and will be further in electric automobile, sky
Between obtain going deep into expansion in terms of the large-scale energy storage field such as technology, national defense industry, its wide application prospect is new clear for accelerating
The successful change of the clean energy is of great significance.
From the angle of application, if exploitation is provided simultaneously with high-energy-density, high power density and high stable circulation
Property feature lithium ion battery material as high-performance energy-storage system direction primary study and the technological core of tackling key problem, then anode material
The core key element that the performance of material is good and bad, cost height is lithium ion battery electrode material.1Whole world lithium ion battery is born at present
Pole material annual requirement is presented stabilized growth, the Compound Annual Growth Rate (CAGR) about 10% between 2008-2014, wherein studying
More carbonaceous negative material is except native graphite (Natural graphite), Delanium (Artifical
Graphite), a phase carbon microspheres (Mesocarbonmicrobeads) also has amorphous pyrolytic carbon (Armorphouspyrolytic
Carbon) etc., former three, which is roughly equal to, accounts for 95% negative material market.And Hitachi's chemical conversion and Shenzhen Bei Terui are roughly equal to and account for the whole world 5 into city
Field occupation rate, but these carbonaceous materials also respectively have its advantage and disadvantage and selectivity to be applicable in.Negative material as embedding lithium earliest
The embedding lithium capacity of theoretical maximum chemistry of petroleum coke is LiC12, electrochemical specific capacity 186mAh/g, there are volumetric expansion during embedding lithium
The shortcomings of reducing battery life, limits it and further develops；Traditional graphite cathode material easily causes layer because of embedding lithium ionic insertion/deinsertion process
Shape structural damage influences the cycle life of battery, and the embedding lithium end-products of interlayer are LiC6, its actual specific capacity (~270mAh/
G) it is less than theoretical value (372mAh/g), the process of intercalation in vertical graphite aspect is difficult, influences circulation performance, limits
Its application in lithium ion battery of new generation.Delanium similar in reversible specific capacity and a phase carbon microspheres be required for by
The superhigh temperature stove graphitization heat treatment of 2400 DEG C and the above can obtain, and cycle life is relatively long, and major defect is specific volume
Potentiality deficiency is measured, the superhigh temperature stove preparation process of high cost is allowed to manufacture cost compared with graphite charcoal higher.In addition, with special
The novel charcoal material such as dimension, two-dimension flexible structure, good electric conductivity and thermal conduction characteristic carbon nanotube, graphene, to lithium-ion electric
The development in pond brings new opportunity, but there is also there is the deficiencies of relatively low coulombic efficiency, voltage lagged part, is not suitable for
Directly as negative material, it is necessary to carry out the amorphisation of appropriate structural modification and Heteroatom doping.
Therefore, the improvement of new carbon cathode material and innovation research cause low cost, high embedding lithium capacity, high-energy-density and
High circulation stability become lithium ion battery key negative material field Key Scientific And Technical Problems, have raw material sources extensively, system
Preparation Method is simple, microstructure is enriched, there is an urgent need for exploitation for high performance new type lithium ion battery carbon cathode material.
The content of the invention
Technical problem：The present invention is intended to provide a kind of method that the porous carbon cathode material of N doping is prepared using organic matter,
Problem to be solved is with itrogenous organic substance, with different activator or template, after charing process, prepares N doping
Porous carbon cathode material, realize cheap itrogenous organic substance efficiently utilize and to provide a kind of new and effective N doping porous
The method of charcoal ion secondary battery and application.
Technical solution：
The present invention is that structure is ground and is blended for the purple cyclic ketones class charcoal source (containing suitable, trans molecule) of 1-34 and template
Thing, the porous carbon cathode material of N doping is prepared through charing process.The technique can overcome in the preparation process of usual nitrating charcoal by
The difficulty of the Effective Doping of nitrogen is difficult to realize in the easy pyrolysis of nitrogen source, ensures nitrogen content in material；This method raw material is easy at the same time
, operation is easy, and a new way is provided for efficient utilize in 5 charcoal source (containing suitable, trans molecule) for low-cost structure
Footpath.
Purple cyclic ketones class nitrogenous condensed ring of the N doping porous charcoal protected in the present invention with nitrogen element content between 7-40%
Aromatic hydrocarbons is charcoal source, with the sodium carbonate in the range of 10 nanometer of -1 cm size or sodium acid carbonate or sodium hydroxide or sodium sulphate or sulfuric acid
Hydrogen sodium or sodium nitrate or sodium chloride or potassium carbonate or saleratus or potassium hydroxide or potassium sulfate or potassium acid sulfate or potassium nitrate or
Potassium chloride or lithium carbonate or lithium bicarbonate or lithium hydroxide or lithium sulfate or lithium hydrogen sulfate or lithium nitrate or lithium chloride or cesium carbonate
Or caesium bicarbonate or cesium hydroxide or cesium sulfate or cesium hydrogen sulfate or cesium nitrate or cesium chloride or calcium carbonate or calcium bicarbonate or hydrogen
Calcium oxide or calcium sulfate or calcium bisulfate or calcium nitrate or calcium chloride or magnesium carbonate or magnesium bicarbonate or magnesium hydroxide or magnesium sulfate
Magnesium bisulfate or magnesium nitrate or magnesium chloride or silica one of which or it is two or more be activator or masterplate, in 300-
In the range of 1500 degree, in nitrogen or the atmosphere of inert gases of argon gas or argon gas-hydrogen mixed gas, heat treatment 30 minutes -72 it is small when,
With deionized water, either hydrochloric acid or hydrofluoric acid or bifluoride hydrogen aqueous ammonium clean activator or template agent, remove molten
Agent, obtain nitrogen element content the amorphous state of 7-40%, bar-shaped, spherical, sheet, acicular micron order, nano-scale particle,
Specific surface area is between 1-4000m2The N doping porous carbon material of/g, as lithium ion either sodium ion or the secondary electricity of magnesium ion
Negative active core-shell material in pond.
The nitrogenous condensed-nuclei aromatics structure charcoal source of purple cyclic ketones class (containing suitable, trans molecule) protected in the present invention is to be preferably as follows knot
Structure 1-34：
Wherein, the compound of cis or trans configuration is included in the state of aggregation of structure shown in cis-/trans representatives.
The N doping porous charcoal protected in the present invention is as follows as the specific method of ion secondary battery negative material：
A. by N doping porous carbon material and additive dispersion mixing in organic solvent, enough organic solvents are added
Afterwards, stir 4-36 it is small when form it into homogeneous slurry, be coated in aluminum foil current collector, the electrode coated is in atmosphere or vacuum
Positive electrode, drying temperature 273-473K are obtained after when drying 4-36 is small in drying box；Then cut with tablet press machine and electrode is made
Piece；Cathode is done with the electrode slice in the glove box full of argon gas, two electrodes are separated with membrane, and the organic solvent solution of lithium salts is done
Electrolyte, using lithium metal or lithium alloys as anode, assembles in argon gas, nitrogen or dry air and obtains lithium ion secondary electricity
Pond.
B. the active material is N doping porous charcoal；Conductive Carbon materials are carbon black or graphite or both mixture；Add
Add agent for graphene, porous carbon, activated carbon, charcoal, aluminium oxide, silica, magnesia, zinc oxide, cupric oxide, chromium oxide, poly-
One or more in tetrafluoroethene or Kynoar are according to the obtained additive package of arbitrary proportion；Organic solvent is two
Methyl sulfoxide, n,N-dimethylacetamide, n,N-Dimethylformamide, sulfolane, propane diols, 1-methyl-2-pyrrolidinone, in oneself
One or more kinds of arbitrary proportions in acid amides, triethylene diamine or 1,5- diazabicyclo [4.3.0] nonyl- 5- alkene obtain mixed
Bonding solvent；The quality share of active material, conductive Carbon materials and additive is 10-90: 10-90: 0-50, organic solvent with
The mass ratio of active material is 1-30: 1；Collector be foam copper, stainless steel foam nickel foam, foamed aluminium, foam iron-nickel alloy,
Foamed iron, copper mesh, copper sheet, iron net, iron plate, aluminium net, aluminium flake, stainless (steel) wire or stainless steel substrates.
C. the lithium alloys are lithium-aluminium alloy, and wherein the weight content of lithium is 10-80%, and membrane is polyethylene, poly- third
Alkene, polyacrylate, polystyrene, polytetrafluoroethylene (PTFE), cellulose, makrolon and the one or more of glass fibre appoint
The mixing membrane for mixed proportion of anticipating；Electrolyte is the solution that solvent is dissolved in by lithium salts, and the concentration of lithium salts in a solvent is 0.1-
2mol/L, wherein lithium salts are the one of lithium perchlorate, LiBF4 or lithium hexafluoro phosphate and double (trimethyl fluoride sulfonyl) imine lithiums
The mixing lithium salts of kind or a variety of any mixed proportions, solvent is ethylene carbonate, propene carbonate, methyl ethyl carbonate, diformazan
Base sulfoxide, n,N-dimethylacetamide, n,N-Dimethylformamide, sulfolane, propane diols, 1-methyl-2-pyrrolidinone, acyl in oneself
Amine, triethylene diamine, 1,5- diazabicyclos [4.3.0] nonyl- 5- alkene, 1,3- dioxanes, 1- methyl -3- alkyl imidazoles salt and 1,
The mixed solvent of one or more any mixed proportions in 2- dimethyl -3- alkyl imidazole salt；Wherein in alkyl imidazole salt
Alkyl for 0 to 40 carbon atom alkyl；Anion is BF4 -、PF6 -、Cl-、F-、SO4 2-、NO3 -、I-、H2PO4 -、ClO4 -、
Ac-、Br-、SbF6 -、CN-、CF3COO-、(CH3SO2)2N-、CH3SO3 -Or CF3SO3 -。
The beneficial effects of the invention are as follows：
Included using purple cyclic ketones class charcoal source as the advantages of preparing N doping porous carbon cathode material：1. big conjugated structure charcoal
Source can improve porous charcoal electric conductivity, improve circulation performance；2. the high nitrogen doped high electricity of conjugation that can also promote porous charcoal
Conductance, the bandwidth energy level for changing Carbon Materials improve carbon activity, are expected to improve potential voltage, and increase the defects of being combined with lithium ion
Avtive spot improves specific capacity；3. porous and special nanostructured prepared by activation method, template, high specific surface area can be with
Ensure the surface reaction ratio of ion and charcoal base, and then realize height ratio capacity, high circulation stability, the nano junction of high-energy-density
Structure, and then improve volume capacity, quality capacity；Conjugated structure fragment interlamellar spacing is slightly larger than graphite layers inside N doping porous charcoal
Away from, be conducive to lithium ion disengaging without causing volumetric expansion to deform the advantages that.
Such N doping porous carbon material can also be applied to Organic Electricities such as the electric storage in energy storage material, ultracapacitors
Subdomains.
Main advantages of the present invention are：
1. charcoal source structure enriches, commercially available or easily prepared；
2. there is good cyclical stability.
Brief description of the drawings：
Fig. 1 using structure as 1-34 in a kind of SEM shape appearance figures of N doping porous charcoal that prepare of purple cyclic ketones class charcoal source
Fig. 2 are porous as the N doping that a kind of purple cyclic ketones class charcoal source in 1-34 prepares under the conditions of template using structure
The SEM shape appearance figures of charcoal
Fig. 3 using structure as in 1-34 a kind of charcoal source prepare N doping charcoal as anode lithium rechargeable battery not
Curve is kept with the cycle charge discharge capacitance under multiplying power；
Fig. 4 is used as anode by the N doping porous charcoal that a kind of charcoal source in 1-34 prepares under the conditions of template of structure
Cycle charge discharge capacitance of the lithium rechargeable battery under different multiplying keeps curve.
Embodiment：
Technical scheme is further described with reference to embodiment, but these embodiments not limit the present invention
Embodiment.Those skilled in the art is in the case of without prejudice to the present application spirit, the scheme Ying Ben that is completed
In the range of invention.
Embodiment 1
In mass ratio for 1: 1 ratio by a kind of charcoal source in 1-34 and sodium hydroxide mixed grinding 10min；Tube furnace
In, under the argon gas atmosphere of 20ml/min, 600 DEG C are warming up to the heating rate of 1 DEG C/min, carbonizes 2h, after washing and drying,
Up to the porous carbon cathode material of N doping.
Embodiment 2
In mass ratio for 1: 1 ratio by a kind of charcoal source in 1-34 and sodium sulphate mixed grinding 10min；In tube furnace,
Under the argon gas atmosphere of 20ml/min, 600 DEG C are warming up to the heating rate of 1 DEG C/min, carbonizes 2h, after washing and drying, i.e.,
Obtain the porous carbon cathode material of N doping.
Embodiment 3
In mass ratio for 1: 1 ratio by a kind of charcoal source in 1-34 and sodium chloride mixed grinding 10min；In tube furnace,
Under the argon gas atmosphere of 20ml/min, 600 DEG C are warming up to the heating rate of 1 DEG C/min, carbonizes 2h, after washing and drying, i.e.,
Obtain the porous carbon cathode material of N doping.
Embodiment 4
In mass ratio for 1: 2 ratio by a kind of charcoal source in 1-34 and sodium sulphate mixed grinding 10min；In tube furnace,
Under the argon gas atmosphere of 20ml/min, 600 DEG C are warming up to the heating rate of 1 DEG C/min, carbonizes 2h, after washing and drying, i.e.,
Obtain the porous carbon cathode material of N doping.
Embodiment 5
In mass ratio for 1: 4 ratio by a kind of charcoal source in 1-34 and sodium sulphate mixed grinding 10min；In tube furnace,
Under the argon gas atmosphere of 20ml/min, 600 DEG C are warming up to the heating rate of 1 DEG C/min, carbonizes 2h, after washing and drying, i.e.,
Obtain the porous carbon cathode material of N doping.
Embodiment 6
In mass ratio for 1: 8 ratio by a kind of charcoal source in 1-34 and sodium sulphate mixed grinding 10min；In tube furnace,
Under the argon gas atmosphere of 20ml/min, 600 DEG C are warming up to the heating rate of 1 DEG C/min, carbonizes 2h, after washing and drying, i.e.,
Obtain the porous carbon cathode material of N doping.
Embodiment 7
In mass ratio for 1: 1 ratio by a kind of charcoal source in 1-34 and silica mixed grinding 10min；Tube furnace
In, under the argon gas atmosphere of 20ml/min, 700 DEG C are warming up to the heating rate of 1 DEG C/min, 2h is carbonized, is washed to remove
SiO2And after drying, up to the porous carbon cathode material of N doping.
Claims (5)
1. preparation method and the application of a kind of porous carbon cathode material of N doping, it is characterised in that：The porous charcoal is contained with nitrogen
It is charcoal source to measure the purple nitrogenous condensed-nuclei aromatics of cyclic ketones class between 7-40%, with the sodium carbonate in the range of 10 nanometer of -1 cm size or
Sodium acid carbonate or sodium hydroxide or sodium sulphate or niter cake or sodium nitrate or sodium chloride or potassium carbonate or saleratus or hydrogen-oxygen
Change potassium or potassium sulfate or potassium acid sulfate or potassium nitrate or potassium chloride or lithium carbonate or lithium bicarbonate or lithium hydroxide or lithium sulfate or
Lithium hydrogen sulfate or lithium nitrate or lithium chloride or cesium carbonate or caesium bicarbonate or cesium hydroxide or cesium sulfate or cesium hydrogen sulfate or nitric acid
Caesium or cesium chloride or calcium carbonate or calcium bicarbonate or calcium hydroxide or calcium sulfate or calcium bisulfate or calcium nitrate or calcium chloride or carbon
Sour magnesium or magnesium bicarbonate or magnesium hydroxide or magnesium sulfate or magnesium bisulfate or magnesium nitrate or magnesium chloride or silica one of which
Or two or more is activator or masterplate, in the range of 300-1500 degree, nitrogen or argon gas or argon gas-hydrogen mixed gas it is lazy
Property atmosphere in, when heat treatment 30 minutes -72 is small, with deionized water either hydrochloric acid or hydrofluoric acid or bifluoride hydrogen ammonium water
Solution cleans activator or template agent, removes solvent, obtain nitrogen element content 7-40% amorphous state, it is bar-shaped, spherical,
Sheet, acicular micron order, nano-scale particle, specific surface area is between 1-4000m2The N doping porous carbon material of/g, as
The lithium ion either negative active core-shell material in sodium ion or magnesium ion secondary cell.
2. preparation method and the application of a kind of N doping porous carbon electrode material as claimed in claim 1, it is characterised in that institute
State the nitrogenous condensed-nuclei aromatics structure charcoal source of purple cyclic ketones class (containing suitable, trans molecule) and be preferably as follows 1-34 structures：
Wherein, the compound of cis or trans configuration is included in the state of aggregation of structure shown in cis-/trans representatives.
3. a kind of a kind of preparation method of porous carbon cathode material of N doping and application as claimed in claim 1, it is characterised in that
Method is as follows：
By N doping porous carbon material and additive dispersion mixing in organic solvent, after adding enough organic solvents, stirring
Homogeneous slurry is formed it into when 4-36 is small, is coated in aluminum foil current collector, the electrode coated is in atmosphere or vacuum drying chamber
Positive electrode, drying temperature 273-473K are obtained after when middle dry 4-36 is small；Then cut with tablet press machine and electrode slice is made；Filling
Cathode is done with the electrode slice in the glove box of full argon gas, two electrodes are separated with membrane, and the organic solvent solution of lithium salts does electrolyte,
Using lithium metal or lithium alloys as anode, assembled in argon gas, nitrogen or dry air and obtain lithium rechargeable battery.
4. a kind of a kind of preparation method of porous carbon cathode material of N doping and application as claimed in claim 1, it is characterised in that
The active material is N doping porous charcoal；Conductive Carbon materials are carbon black or graphite or both mixture；Additive is graphite
Alkene, porous carbon, activated carbon, charcoal, aluminium oxide, silica, magnesia, zinc oxide, cupric oxide, chromium oxide, polytetrafluoroethylene (PTFE) or
One or more in Kynoar are according to the obtained additive package of arbitrary proportion；Organic solvent for dimethyl sulfoxide (DMSO),
N,N-dimethylacetamide, n,N-Dimethylformamide, sulfolane, propane diols, 1-methyl-2-pyrrolidinone, caprolactam, three second
The mixed solvent that one or more kinds of arbitrary proportions in alkene diamines or 1,5- diazabicyclo [4.3.0] nonyl- 5- alkene obtain；It is living
Property material, conductive Carbon materials and additive quality share be 10-90: 10-90: 0-50, organic solvent and active material
Mass ratio is 1-30: 1；Collector is foam copper, stainless steel foam nickel foam, foamed aluminium, foam iron-nickel alloy, foamed iron, copper
Net, copper sheet, iron net, iron plate, aluminium net, aluminium flake, stainless (steel) wire or stainless steel substrates.
5. preparation method and the application of the porous carbon cathode material of a kind of N doping according to claim 4, it is characterised in that
The lithium alloys are lithium-aluminium alloy, and wherein the weight content of lithium is 10-80%, and membrane is polyethylene, polypropylene, polyacrylic acid
Ester, polystyrene, polytetrafluoroethylene (PTFE), cellulose, one or more any mixed proportions of makrolon and glass fibre
Mix membrane；Electrolyte is the solution that solvent is dissolved in by lithium salts, and the concentration of lithium salts in a solvent is 0.1-2mol/L, wherein lithium
Salt is the one or more any of lithium perchlorate, LiBF4 or lithium hexafluoro phosphate and pair (trimethyl fluoride sulfonyl) imine lithiums
The mixing lithium salts of mixed proportion, solvent is ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl sulfoxide (DMSO), N, N- diformazans
Yl acetamide, n,N-Dimethylformamide, sulfolane, propane diols, 1-methyl-2-pyrrolidinone, caprolactam, triethylene diamine, 1,
5- diazabicyclos [4.3.0] nonyl- 5- alkene, 1,3- dioxanes, 1- methyl -3- alkyl imidazoles salt and 1,2- dimethyl -3- alkyl
The mixed solvent of one or more any mixed proportions in imidazole salts；Alkyl wherein in alkyl imidazole salt is 0 to 40
The alkyl of carbon atom；Anion is BE4 -、PF6 -、Cl-、F-、SO4 2-、NO3 -、I-、H2PO4 -、ClO4 -、Ac-、Br-、SbF6 -、CN-、
CF3COO-、(CH3SO2)2N-、CH3SO3 -Or CF3SO3 -。
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| CN108565447A (en) * | 2018-07-09 | 2018-09-21 | 天津工业大学 | A kind of preparation method of high specific energy porous silicon charcoal composite negative pole material |
| CN110364733A (en) * | 2019-06-05 | 2019-10-22 | 江西力能新能源科技有限公司 | A kind of anode plate for lithium ionic cell containing conductive coating |
| CN111634909A (en) * | 2020-05-22 | 2020-09-08 | 上海应用技术大学 | Preparation method and application of nitrogen-doped porous carbon material based on trichloro-aza-acene fused-ring aromatic hydrocarbon |
| CN112072062A (en) * | 2020-09-04 | 2020-12-11 | 西北工业大学 | Multi-carbonyl aza-condensed ring material for proton battery and preparation method of electrode thereof |
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| CN108565447A (en) * | 2018-07-09 | 2018-09-21 | 天津工业大学 | A kind of preparation method of high specific energy porous silicon charcoal composite negative pole material |
| CN110364733A (en) * | 2019-06-05 | 2019-10-22 | 江西力能新能源科技有限公司 | A kind of anode plate for lithium ionic cell containing conductive coating |
| CN113299981A (en) * | 2020-02-21 | 2021-08-24 | 广州天赐高新材料股份有限公司 | Solid polymer electrolyte membrane, preparation method and application thereof |
| CN111634909A (en) * | 2020-05-22 | 2020-09-08 | 上海应用技术大学 | Preparation method and application of nitrogen-doped porous carbon material based on trichloro-aza-acene fused-ring aromatic hydrocarbon |
| CN111634909B (en) * | 2020-05-22 | 2021-09-24 | 上海应用技术大学 | Preparation method and application of nitrogen-doped porous carbon material based on trichloro-aza-acene fused-ring aromatic hydrocarbon |
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| CN112194663A (en) * | 2020-10-30 | 2021-01-08 | 北京燕化集联光电技术有限公司 | Novel electronic transmission material and application thereof |
| CN112341465A (en) * | 2020-10-30 | 2021-02-09 | 北京燕化集联光电技术有限公司 | Novel polyheterocyclic compound and application thereof |
| CN112194663B (en) * | 2020-10-30 | 2021-11-09 | 北京燕化集联光电技术有限公司 | Novel electronic transmission material and application thereof |
| CN112300175A (en) * | 2020-10-30 | 2021-02-02 | 北京燕化集联光电技术有限公司 | Multi-heterocyclic compound and application thereof |
| CN112908718A (en) * | 2021-01-22 | 2021-06-04 | 滁州学院 | Three-dimensional mutual crosslinking nitrogen-doped acicular carbon, preparation method and application |
| CN113735100A (en) * | 2021-09-07 | 2021-12-03 | 河北省科学院能源研究所 | Method for activating two-dimensional nitrogen-doped graphene |
| CN113735100B (en) * | 2021-09-07 | 2023-05-02 | 河北省科学院能源研究所 | Method for activating two-dimensional nitrogen-doped graphene |
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| CN114715877A (en) * | 2022-04-20 | 2022-07-08 | 嘉应学院 | High-specific-surface-area porous carbon material and preparation method thereof |
| CN114715877B (en) * | 2022-04-20 | 2023-08-11 | 嘉应学院 | Porous carbon material with high specific surface area and preparation method thereof |
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