CN115050582A - Porous carbon support composite lithium extraction electrode and preparation method thereof - Google Patents
Porous carbon support composite lithium extraction electrode and preparation method thereof Download PDFInfo
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- CN115050582A CN115050582A CN202210694368.7A CN202210694368A CN115050582A CN 115050582 A CN115050582 A CN 115050582A CN 202210694368 A CN202210694368 A CN 202210694368A CN 115050582 A CN115050582 A CN 115050582A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 94
- 238000000605 extraction Methods 0.000 title claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 229920005546 furfural resin Polymers 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229960004011 methenamine Drugs 0.000 claims description 2
- 239000000467 phytic acid Substances 0.000 claims description 2
- 229940068041 phytic acid Drugs 0.000 claims description 2
- 235000002949 phytic acid Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229910010710 LiFePO Inorganic materials 0.000 description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000002687 intercalation Effects 0.000 description 10
- 238000009830 intercalation Methods 0.000 description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000012267 brine Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- -1 aerospace Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000003361 porogen Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a porous carbon support composite lithium extraction electrode and a preparation method thereof. Mixing the lithium extraction active component or a precursor thereof with a pore-forming agent, a regulator and an organic high molecular polymer monomer, carrying out in-situ polymerization reaction on the high molecular monomer under the catalysis of acid or alkali, and carrying out curing molding in a mold. And (3) carrying out high-temperature roasting in-situ conversion on the formed material under an anaerobic condition, and removing the pore-foaming agent by acid and alkali treatment to obtain the porous carbon support composite lithium extraction electrode. The lithium extraction composite electrode prepared by the invention has the advantages of simple synthesis method and good stability, not only effectively solves the problem of electrode material falling off in the preparation of the electrode by the traditional coating method, but also can obviously improve the conductivity, lithium extraction capacity and rate of the electrode, thereby being beneficial to promoting the large-scale preparation of the lithium extraction electrode and the industrial popularization and application of the electrochemical lithium extraction technology.
Description
Technical Field
The invention belongs to the technical field of lithium extraction, and particularly relates to a porous carbon support composite lithium extraction electrode and a preparation method thereof.
Background
Lithium is taken as energy metal in the 21 st century and is widely applied to the fields of lubricants, aerospace, glass, ceramics, lithium batteries and the like. In recent years, with rapid development of industries such as portable devices and electric vehicles, the demand for lithium resources has increased year by year. Although the process for extracting lithium from solid ore is mature, the problems of high energy consumption, heavy pollution and the like exist. The reserves of brine type liquid lithium ores such as salt lake brine, underground brine and the like are absolutely superior in various types of lithium ores. Because of the scale and cost advantages of lithium extraction from brine, lithium recovery from liquid lithium ore becomes a research hotspot in the global lithium extraction industry.
According to the different compositions and characteristics of different liquid lithium ores, lithium extraction technologies such as a precipitation method, a solvent extraction method, an adsorption method, a membrane separation method, an electrochemical method and the like are developed. Compared with other methods, the electrochemical method attracts people's attention due to its advantages of good selectivity, environmental protection and the like. How to efficiently and stably extract lithium from liquid lithium ore becomes the key point of attention of electrochemical lithium extraction technology.
The quality of the electrode performance is the key of the electrochemical lithium extraction technology. When electrochemical extraction of lithium is carried out in aqueous solution, active components (such as LiFePO) are firstly needed 4 、LiMn 2 O 4 Etc.) are prepared into a specific shape. In order to obtain a high-performance lithium extraction electrode, related research has been carried out. CN113278819A discloses a high-selectivity and hydrophilic electrode and a preparation method thereof, which improves the hydrophilicity of polyvinylidene fluoride (PVDF) as a binder and improves the mass transfer of a solution in the electrode; CN113293285B discloses a preparation method of a modified lithium extraction electrode of a fast ion conductor, which effectively improves the selectivity and the cycle performance of the electrode; CN113293312B discloses a preparation method of a composite porous electrode for lithium extraction, wherein the hydrophilicity of the electrode is improved by using a water-based binder to replace PVDF, and the structural strength of the electrode is improved by adding a fiber structure reinforcing agent; CN113293291B discloses a high-conductivity lithium extraction methodAccording to the electrode preparation method, the electrode active substance is modified by adopting the high-molecular conductive polymer, so that the electrode with a porous-microcrack internal structure is prepared, and the hydrophilicity, the conductivity and the lithium extraction rate of the electrode are effectively improved.
As disclosed in the related patent art or research report, in the preparation of an electrode, an active material is applied to a current collector mainly using a polymer such as PVDF as a binder. However, the binder has poor lithium ion conductivity due to its high crystallinity and low surface energy, and the lithium extraction capacity of the electrode is reduced due to the use of the current collector and the binder. In addition, the electrode obtained by the coating method has stability problems such as falling-off of the electrode material. In view of this, the development of the electrode with high lithium extraction rate and high stability and the preparation method thereof have important significance for the development of brine type liquid lithium ore resources.
Disclosure of Invention
In order to overcome the defects of the lithium extraction electrode prepared by the traditional coating method, the invention provides the porous carbon support composite lithium extraction electrode with excellent electrochemical lithium extraction performance and high stability and the preparation method thereof.
The innovation points of the invention are as follows: by the innovative means of resin in-situ polymerization and high-temperature carbonization conversion, a novel resin-based porous carbon in-situ support lithium extraction electrode without a current collector and a binder is developed, and another simple and low-cost lithium extraction electrode preparation method is developed.
The technical scheme and the technical process provided by the invention are as follows:
the method comprises the following steps:
1) mixing the lithium extracting active component or the precursor thereof, a pore-forming agent, a regulator and an organic high molecular polymer monomer.
2) The polymer monomers in the mixture are polymerized under the action of acid or alkali, and are solidified and formed in a mould.
3) And roasting the cured and molded material under an anaerobic condition, converting the organic polymer into a carbon support in situ, and synchronously converting the precursor of the lithium extraction active component into the lithium extraction active component in situ.
4) And (3) soaking the roasted material in acid and alkali to remove the pore-forming agent, thereby obtaining the porous carbon support composite lithium extraction electrode.
In the step 1), the lithium extraction active component is lithium iron phosphate (LiFePO) 4 ) Lithium vanadium phosphate (Li) 3 V 2 (PO 4 ) 3 ) Lithium manganate (LiMn) 2 O 4 ) One or more than two of them.
In step 1), the precursors of the lithium extraction active component include a lithium source, an iron source, a vanadium source, a manganese source, and a phosphorus source. Wherein, the lithium source, the iron source, the vanadium source and the manganese source comprise one or more than two of oxides, hydroxides, chlorides, sulfates, carbonates and acetates of various metals; the phosphorus source comprises one or more of phosphate, hydrogen phosphate, dihydrogen phosphate and phytic acid.
In step 1), the porogen is an inorganic salt, preferably one or more of ammonium salt, carbonate, bicarbonate and hydroxide. Further, the porogen is preferably ammonium carbonate or ammonium bicarbonate.
In the step 1), the regulator is one or more than two of polyethylene glycol, cetyl trimethyl ammonium bromide, hexamethylene tetramine, benzene sulfonic acid and dodecyl benzene sulfonic acid. The function of the regulator is to improve the curing rate of the composite material and the dispersibility of the lithium extraction active ingredient in the material.
In step 1), the high molecular polymer comprises one or more of phenolic resin, urea resin, melamine-formaldehyde resin and furfural resin.
In the step 1), the lithium extraction active component or the precursor thereof, the pore-forming agent, the regulator and the organic high molecular polymer monomer respectively account for 10-70%, 0-10% and 30-80% of the total mass. Preferably, the weight percentage of the total weight is 40% -60%, 0% -6% and 40% -60%.
In step 2), the preferable acid is one or more of sulfuric acid, phosphoric acid, hydrochloric acid and acetic acid; the preferable alkali is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia water.
In addition, in the step 3), the roasting temperature is 400-800 ℃ and the time is 3-8 h. Preferably, the roasting temperature is 500-700 ℃ and the time is 4-7 h. Temperatures below 400 c or times less than 3 hours may result in insufficient carbonization of the material.
The invention has the advantages and positive effects that:
the porous carbon supported composite lithium extraction electrode prepared by the invention takes carbon as a support body and a conductive agent, and forms a good conductive network. Compared with the electrode prepared by the traditional coating method, the method does not use any binder, and the electrode has high porosity and specific surface area, so that the lithium extraction rate and capacity of the electrode are improved, and the problem of poor stability of the electrode prepared by the traditional coating method is effectively solved. In addition, the electrode preparation method disclosed by the invention has the advantages of simple process, low cost and the like, and is easy for industrial batch production.
Drawings
FIG. 1 is a flow chart of the preparation of an electrode in example 1.
Fig. 2(a) is an XRD pattern of the electrode prepared in example 1.
Fig. 2(B) is an SEM image of the electrode prepared in example 1.
FIG. 3 is a graph showing the change of lithium intercalation capacity with time during the extraction of lithium from the electrode prepared in example 1.
FIG. 4 is a graph showing the change of lithium intercalation capacity with time during the extraction of lithium from the electrode prepared in example 2.
FIG. 5 is a graph showing the change of lithium intercalation capacity with time during the extraction of lithium from the electrode prepared in example 3.
FIG. 6 is a graph showing the change of the lithium intercalation capacity with time during the extraction of lithium from the electrode prepared in example 4.
Fig. 7(a) is an SEM image of the electrode prepared in example 5.
Fig. 7(B) is a graph showing the lithium extraction stability of the electrode prepared in example 5.
FIG. 8(A) is an SEM photograph (scale: 1mm) of the electrode prepared in example 6.
FIG. 8(B) is an SEM photograph (scale: 10 μm) of the electrode fabricated in example 6.
Fig. 9(a) is an SEM image of an electrode prepared by the coating method in comparative example 1.
FIG. 9(B) is a graph showing the change of lithium intercalation capacity with time during the extraction of lithium from the electrode prepared by the coating method in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are illustrative only and not limiting, and the scope of the present invention is not limited thereby.
Example 1:
taking phenolic resin as a carbon source, (NH) 4 ) 2 CO 3 As a porogen, LiFePO 4 LiOH.H as a precursor of (1) 2 O、FeCl 3 ·6H 2 O and NH 4 H 2 PO 4 Synthesizing LiFePO as raw material under the action of alkali 4 And (3) a composite electrode.
The electrode preparation process is shown in FIG. 1. Taking 0.02mol of LiOH H 2 O (as both precursor raw material and basic catalyst) was dissolved in an appropriate amount of water, and 0.01mol of resorcinol and 3mL of formaldehyde solution were added to the above solution. Taking 0.02mol of NH 4 H 2 PO 4 、0.02mol FeCl 3 ·6H 2 O and an appropriate amount of (NH) 4 ) 2 CO 3 (accounting for 6 percent of the mass of the electrode), uniformly grinding, pouring into the solution, stirring until the solution is in a jelly shape, and injecting into an electrode silica gel mold. And (3) placing the silica gel mold in an oven for drying and shaping, wherein the temperature of the oven is set to be 80 ℃, and the drying time is 6 h. Then roasting in a tube furnace at 700 ℃ for 8h under the oxygen-free condition. Cooling to room temperature, sequentially placing the electrode in 1mol/LHCl and NaOH to soak for 4h respectively to remove the pore-foaming agent, thus obtaining the porous carbon supported LiFePO 4 And (3) a composite electrode.
The XRD and SEM images of the resulting electrode are shown in FIG. 2(A) and FIG. 2 (B). As can be seen from the figure, LiFePO was successfully synthesized by in-situ simultaneous conversion 4 And LiFePO 4 Well dispersed on the carbon support material. For 100mg/L Li + The extraction was carried out, and the change of the lithium intercalation capacity with time during the lithium extraction is shown in FIG. 3. As can be seen from the figure, the lithium extraction balance time of the electrode is less than 2h, and the balance lithium insertion capacity is close to 4mg/cm 3 。
Example 2:
takes phenolic resin as a carbon source, polyethylene glycol (PEG6000) as a regulator and LiFePO 4 LiOH.H as a precursor of (1) 2 O、FeCl 3 ·6H 2 O and NH 4 H 2 PO 4 Synthesizing LiFePO as raw material under the action of alkali 4 And (3) a composite electrode.
The preparation method is similar to that of example 1, and the main difference is that the regulator polyethylene glycol (accounting for 6 percent of the mass of the electrode) is used for replacing the pore-foaming agent (NH) in example 1 4 ) 2 CO 3 . The lithium intercalation capacity with time during the extraction of lithium from the resulting electrode is shown in FIG. 4. As can be seen from the figure, the lithium extraction equilibrium time of the electrode is less than 1.5h, and the equilibrium lithium insertion capacity is about 5mg/cm 3 。
Example 3:
takes phenolic resin as a carbon source and LiFePO 4 Precursor LiCl, FeCl 3 ·6H 2 O and NH 4 H 2 PO 4 Synthesizing LiFePO by taking raw materials (without pore-forming agent and regulator) under the action of acid 4 And (3) a composite electrode.
Weighing NH according to the molar ratio of 1.05:1.05:1 4 H 2 PO 4 (as both precursor raw material and acid catalyst), LiCl and FeCl 3 ·6H 2 Dissolving O in a proper amount of water to obtain a solution A; weighing resorcinol and formaldehyde solution according to the phenolic aldehyde ratio of 1:0.95, and adding a proper amount of water to obtain solution B. Solution B was poured into solution A (LiFePO in the control electrode) 4 Content of 20%), stirring, and injecting into a silica gel mold. The subsequent steps were the same as in example 1. The lithium intercalation capacity of the resulting electrode during lithium extraction varies with time as shown in FIG. 5. As can be seen from the figure, the adsorption capacity of the obtained electrode is also close to 5mg/cm by using acid as the catalyst for the polymerization reaction of the polymer 3 。
Example 4:
takes phenolic resin as a carbon source and directly takes LiFePO 4 Synthesizing LiFePO under the action of alkali for extracting effective components of lithium 4 And (3) a composite electrode.
The preparation method is similar to that of example 1, and the main difference is that LiFePO is used 4 Substitute for LiOH. H 2 O、NH 4 H 2 PO 4 And FeCl 3 ·6H 2 And (O). In the process of high molecular polymerization, 0.01mol/LNaOH is used as a catalyst. The lithium intercalation capacity of the resulting electrode during lithium extraction varies with time as shown in FIG. 6. As can be seen from the figure, the LiFePO is directly used 4 For extracting the effective components of lithium, the equilibrium lithium intercalation capacity is close to 3.5mg/cm 3 。
Example 5:
LiFePO by using melamine-formaldehyde resin as carbon source 4 Precursor LiCl, FeCl 3 ·6H 2 O and NH 4 H 2 PO 4 Synthesizing LiFePO as raw material under the action of acid 4 And (3) a composite electrode.
Weighing NH according to the molar ratio of 1.05:1.05:1 4 H 2 PO 4 LiCl and FeCl 3 ·6H 2 Dissolving O in a proper amount of water to obtain a solution A; and weighing melamine, resorcinol and formaldehyde according to the molar ratio of 1:30 of melamine to resorcinol and the phenolic aldehyde ratio of 1:1.4, and adding a proper amount of water to dissolve to obtain a solution B. Solution B was poured into solution A (LiFePO in the control electrode) 4 Content 30%), stirred well and poured into a silica gel mold. The subsequent steps were the same as in example 1. The SEM image of the obtained electrode is shown in FIG. 7(A), and the stability of lithium extraction by cycling is shown in FIG. 7 (B). As can be seen from the figure, the synthesized LiFePO 4 The lithium ion battery is uniformly dispersed in the carbon support, the prepared electrode has high cycling stability, and the lithium insertion capacity of the electrode is not obviously attenuated after 12 cycles.
Example 6:
melamine-formaldehyde resin is used as a carbon source, LiMn 2 O 4 Synthesizing LiMn under the action of acid for extracting lithium active component 2 O 4 And (3) a composite electrode.
The preparation method is similar to that of example 5, and the main difference is that LiMn is used 2 O 4 Substitute for NH 4 H 2 PO 4 LiCl and FeCl 3 ·6H 2 And O. In the process of high polymer polymerization, 0.01mol/LHCl is used as a catalyst. SEM images of the prepared electrode are shown in FIG. 8(A) and FIG. 8 (B). As can be seen from the figure, LiMn 2 O 4 Successfully loaded on a carbon support.
Comparative example 1:
preparation of LiFePO by coating method 4 Electrode for electrochemical cell
Weighing NH according to the molar ratio of 1.05:1.05:1 4 H 2 PO 4 LiCl and FeCl 3 ·6H 2 And O, weighing 20% of sucrose, mixing the materials, and uniformly grinding. Placing the obtained material in a tubular furnace, roasting for 8h at 700 ℃ under an anaerobic condition to obtain carbon-coated LiFePO 4 . Weighing acetylene black, PVDF and prepared carbon-coated LiFePO according to the mass ratio of 1:1:8 4 After grinding uniformly, N-methylpyrrolidone is slowly added, the obtained slurry is coated on a carbon plate current collector with the same size as the electrode in the embodiment 1, and then the carbon plate current collector is dried at 70 ℃ for 10 hours to obtain the coated electrode. SEM image of the coated electrode, see fig. 9(a), and the lithium insertion capacity of the electrode as a function of time, see fig. 9 (B). As can be seen from the figure, the electrode, LiFePO, was prepared by a coating method 4 Agglomeration phenomenon appears, and the lithium extraction capacity of the electrode prepared by the coating method is less than 3mg/cm 3 。
While embodiments of the present invention have been shown and described, modifications and variations will occur to those skilled in the art in light of the foregoing description. For example, other organic polymer materials are used as carbon sources of the composite material; or directly adopting organic solvent to dissolve or soften high-molecular polymer, then adding lithium-extracting active substance or its precursor and making high-temp. roasting. All such modifications and variations are intended to be included herein within the scope of this disclosure and the appended claims.
Claims (8)
1. A preparation method of a porous carbon support composite lithium extraction electrode is characterized by comprising the following steps: the method comprises the following steps:
1) uniformly mixing the lithium extraction active component or a precursor thereof, a pore-forming agent, a regulator and an organic high molecular polymer monomer according to the proportion of 10-70%, 0-10% and 30-80% of the total mass of the mixture respectively; polymerizing the polymer monomers in the mixture under the action of acid or alkali, and curing and molding in a mold;
2) roasting the cured and molded material for 3-8 h at 400-800 ℃ under an oxygen-free condition;
3) soaking the roasted material in acid and alkali to remove the pore-forming agent, and obtaining a porous carbon support composite lithium extraction electrode;
the active component for extracting lithium is LiFePO 4 、Li 3 V 2 (PO 4 ) 3 、LiMn 2 O 4 One or more than two of the above;
the pore-foaming agent is one or more than two of ammonium salt, carbonate, bicarbonate and hydroxide;
the regulator is one or more than two of polyethylene glycol, cetyl trimethyl ammonium bromide, hexamethylene tetramine, benzene sulfonic acid and dodecyl benzene sulfonic acid;
the high molecular polymer is one or more than two of phenolic resin, urea-formaldehyde resin, melamine-formaldehyde resin and furfural resin.
2. The method of claim 1, wherein: in the step 1), precursors of lithium extraction active components comprise a lithium source, an iron source, a vanadium source, a manganese source and a phosphorus source; wherein, the lithium source, the iron source, the vanadium source and the manganese source comprise one or more than two of oxides, hydroxides, chlorides, sulfates, carbonates and acetates of various metals; the phosphorus source comprises one or more of phosphate, hydrogen phosphate, dihydrogen phosphate and phytic acid.
3. The method of claim 1, wherein: the acid in the step 1) is one or more than two of sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and dihydric phosphate; the alkali is one or more than two of lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia water.
4. The method of claim 1, wherein: the lithium extraction active component or the precursor thereof, the pore-forming agent, the regulator and the organic high molecular polymer monomer account for 40-60%, 0-6% and 40-60% of the total mass of the mixture.
5. The method of claim 1, wherein: the pore-forming agent is ammonium carbonate or ammonium bicarbonate.
6. The method of claim 1, wherein: the roasting temperature is 500-700 ℃, and the roasting time is 4-7 h.
7. A porous carbon supported composite lithium extraction electrode prepared by the method of any one of claims 1 to 6.
8. Use of the porous carbon-supported composite lithium extraction electrode of claim 7 for electrochemical lithium extraction.
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