CN106816595A - A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon - Google Patents
A kind of lithium ion battery coats di-iron trioxide negative material and preparation method thereof with nitrogen-doped carbon Download PDFInfo
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- CN106816595A CN106816595A CN201710137659.5A CN201710137659A CN106816595A CN 106816595 A CN106816595 A CN 106816595A CN 201710137659 A CN201710137659 A CN 201710137659A CN 106816595 A CN106816595 A CN 106816595A
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- iron trioxide
- sio
- fusiformis
- nitrogen
- doped carbon
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- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000005253 cladding Methods 0.000 claims abstract description 16
- 239000011229 interlayer Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims abstract description 14
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims abstract description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 48
- 229910052906 cristobalite Inorganic materials 0.000 claims description 48
- 229910052682 stishovite Inorganic materials 0.000 claims description 48
- 229910052905 tridymite Inorganic materials 0.000 claims description 48
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 230000004323 axial length Effects 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Chemical class 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Chemical class 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Chemical class 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229920005575 poly(amic acid) Chemical class 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001230 potassium iodate Substances 0.000 claims description 2
- 229940093930 potassium iodate Drugs 0.000 claims description 2
- 235000006666 potassium iodate Nutrition 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- CWHNXFAPZCFFJM-UHFFFAOYSA-N [Si+4].[O-2].[O-2].[O-2].[Fe+2].[Fe+2] Chemical compound [Si+4].[O-2].[O-2].[O-2].[Fe+2].[Fe+2] CWHNXFAPZCFFJM-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PLZNPHDJGFDNRM-UHFFFAOYSA-M O.[Na+].[O-][PH2]=O Chemical compound O.[Na+].[O-][PH2]=O PLZNPHDJGFDNRM-UHFFFAOYSA-M 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 2
- IYHRTBGVUHKQKG-UHFFFAOYSA-M [Li+].[O-2].[O-2].[OH-].[Fe+2].[Fe+2] Chemical compound [Li+].[O-2].[O-2].[OH-].[Fe+2].[Fe+2] IYHRTBGVUHKQKG-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of lithium ion battery di-iron trioxide negative material and preparation method thereof is coated with nitrogen-doped carbon, it is as presoma after the outer surface coated silica layer of nanometer fusiformis di-iron trioxide, again one layer of electric polypyrrole is coated in silicon dioxide layer outer surface, the last annealed nitrogen-doped carbon cladding di-iron trioxide negative material for making polypyrrole carbonization, etched removal silica interlayer, i.e. acquisition carry interlayer gap structure.The composite cathode material for lithium ion cell that the present invention is provided can keep circulation volume high, excellent cyclical stability and high magnification (high current density discharge and recharge) performance in the large temperature range including including room temperature, with good application prospect.
Description
Technical field
The present invention relates to one kind can charging-discharging lithium ion battery negative material and preparation method thereof, belong to electrochemical power source neck
Domain.
Background technology
In face of currently increasingly urgent energy and environment problem, the lithium secondary battery for developing efficient stable turns into when business
It is anxious.Lithium ion battery have high-energy-density, long circulation life, it is environment-friendly the features such as, be widely used in portable electronic product
The field such as product and power or energy-storage battery.At present, commercial li-ion battery graphite cathode material specific capacity is relatively low, high rate performance
Difference, and there is larger potential safety hazard, therefore develop focus of the new negative material as the current research field.In recent years
Come, it is increasingly deep with Study on Li-ion batteries, it has been found that, transition metal oxide (di-iron trioxide) has theoretical ratio
Capacity is high, rich content, the advantage such as pollution-free, can be used as the negative material of lithium secondary battery.However, di-iron trioxide is used as lithium
While cell negative pole material highlights advantage, some shortcomings are there is also：1) body phase di-iron trioxide poorly conductive, is unfavorable for electronics
Transmission；2) in charge and discharge process, the easy efflorescence of body phase di-iron trioxide is reunited, and causes cycle performance of battery drastically to decline.
Therefore, improve di-iron trioxide urgently to be excavated as the method for lithium ion battery negative material performance.
The content of the invention
The present invention is to avoid the weak point existing for above-mentioned prior art, there is provided a kind of lithium ion battery is mixed with nitrogen
Miscellaneous carbon coating di-iron trioxide negative material and preparation method thereof, it is intended to improve its electric conductivity, avoid its agglomeration, to improve
The storage lithium performance of material.
The present invention solves technical problem, adopts the following technical scheme that：
Di-iron trioxide negative material is coated with nitrogen-doped carbon the invention discloses a kind of lithium ion battery, it is in nanometer
As presoma after the outer surface coated silica layer of fusiformis di-iron trioxide, then one layer is coated in silicon dioxide layer outer surface
Electric polypyrrole, it is finally annealed to make polypyrrole carbonization, etched removal silica interlayer, that is, obtain with interlayer space knot
The nitrogen-doped carbon cladding di-iron trioxide negative material of structure.
Preferably, the 100~3000nm of axial length long of the nanometer fusiformis di-iron trioxide, short axle 50~1800nm long, folder
Layer gap structure 5~30nm of thickness, N doping carbon-coating is the amorphous graphite of 20~35nm of thickness；Three oxygen are coated in the nitrogen-doped carbon
The weight/mass percentage composition for changing nitrogen-doped carbon in two iron negative materials is 34%~45%.
Above-mentioned lithium ion battery coats the preparation method of di-iron trioxide negative material, including following step with nitrogen-doped carbon
Suddenly：
A, by solvent thermal reaction synthesize nanometer fusiformis di-iron trioxide；
B, in the basic conditions, two are coated by sol-gel process in the outer surface of the nanometer fusiformis di-iron trioxide
Silicon oxide layer, obtains fusiformis presoma Fe2O3@SiO2；
C, the fusiformis presoma Fe is modified with high molecular surfactant2O3@SiO2, then add pyrrole monomer and
Initiator is reacted, and makes fusiformis presoma Fe after modification2O3@SiO2Outer surface coats one layer of electric polypyrrole, obtains Fe2O3@
SiO2@Ppy；
D, under atmosphere of inert gases to the Fe2O3@SiO2@Ppy are made annealing treatment, and polypyrrole is carbonized, and are obtained
Fe2O3@SiO2@C；
E, by the Fe2O3@SiO2@C are performed etching in being put into alkaline solution, to remove SiO2, that is, obtain empty with interlayer
The nitrogen-doped carbon cladding di-iron trioxide negative material Fe of gap structure2O3@C。
Above-mentioned preparation method is specifically carried out as follows：
A, by solvent thermal reaction synthesize nanometer fusiformis di-iron trioxide：
By in the mixed liquor of ferric trichloride and sodium dihydrogen phosphate or sodium hypophosphite addition water and ethanol, reaction solution is obtained；
The concentration of ferric trichloride is 0.015~0.02mol/L in the reaction solution, and the concentration of sodium dihydrogen phosphate or sodium hypophosphite is
0.1~0.5mmol/L；In the mixed liquor of water and ethanol, the percentage by volume of ethanol is 0-50%；
By in reaction solution addition reactor, then 98~105 DEG C of 48~168h of hydro-thermal reaction are so cooled to room temperature
Afterwards, it is centrifuged, washs, that is, obtains nanometer fusiformis di-iron trioxide.
B, 50mg nanometers of fusiformis di-iron trioxide is dispersed in 100mL~200mL by isopropyl alcohol and water by volume 4:1 structure
Into mixed liquor in, then 10~60min of ultrasonic agitation is adding 1~5mL ammoniacal liquor and 0.1mL~0.6mL just under agitation
Tetraethyl orthosilicate, continues to stir 4~24h, and centrifugation, washing obtain fusiformis presoma Fe2O3@SiO2；
C, the fusiformis presoma Fe for being obtained step B2O3@SiO2Be dispersed in 100mL ethanol, be subsequently adding 0.5g~
3.2g high molecular surfactants, stir 12~48h, and centrifugation, washing complete high molecular surfactant modification；
Fusiformis presoma Fe after modifying2O3@SiO2It is scattered in 25mL deionized waters, is subsequently adding 0.18~0.3mL pyrroles
Monomer, ultrasonic 30min are coughed up, then is added dropwise over the initiator solution that 25mL concentration is 15~27mmol/L under agitation, most
4~12h of post-polymerization, is centrifuged, washs, dries, that is, obtain Fe2O3@SiO2@Ppy；
D, by the Fe2O3@SiO2@Ppy are placed in atmosphere of inert gases, are warming up to the heating rate of 2 DEG C -5 DEG C/min
550 DEG C -650 DEG C, anneal 2~4h, polypyrrole is carbonized, and obtains Fe2O3@SiO2@C；
E, by the Fe2O3@SiO2@C are performed etching in being put into alkaline solution, to remove SiO2, that is, obtain empty with interlayer
The nitrogen-doped carbon cladding di-iron trioxide negative material Fe of gap structure2O3@C。
Preferably, the high molecular surfactant be polyvinylpyrrolidone, poly amic acid, hydroxyethyl cellulose and
At least one in polyoxyethylene analog copolymer.
Preferably, the initiator be ammonium persulfate, ferric trichloride, hydrogen peroxide, potassium bichromate and Potassiumiodate at least
It is a kind of.
Preferably, the alkaline solution described in step E is sodium hydroxide solution or potassium hydroxide solution.
Beneficial effects of the present invention are embodied in：
1st, the composite cathode material for lithium ion cell that invention is provided improves the conduction of active material by the compound of carbon nitrogen
Property, in addition, the expansion of volume is provided when the cavity between the carbon-coating and di-iron trioxide of N doping is for active material Li insertion extraction
The useful space, it is therefore prevented that the efflorescence of di-iron trioxide is reunited；Negative material of the invention can be including including room temperature larger temperature
Circulation volume high, the cycle performance of stabilization and good high magnification (high current density discharge and recharge) performance are kept in the range of degree,
Have a good application prospect.
2nd, the transition metal oxide in negative material of the present invention is di-iron trioxide, extensive, inexpensive with raw material sources
It is easy to get, the advantage that preparation process is simple is easily amplified.
Brief description of the drawings
Fig. 1 is the gained nanometer fusiformis di-iron trioxide Fe of the embodiment of the present invention 12O3(Fig. 1 (a)) and nitrogen-doped carbon cladding three
Aoxidize two iron negative material (Fe2O3@C) (Fig. 1 (b)) optical photograph.
Fig. 2 is the gained nanometer fusiformis di-iron trioxide Fe of the embodiment of the present invention 12O3Scanning electron microscope (SEM) photograph (Fig. 2 (a)) and thoroughly
Penetrate electron microscope (Fig. 2 (b)).
Fig. 3 is the gained nitrogen-doped carbon of the embodiment of the present invention 1 cladding di-iron trioxide negative material (Fe2O3@C) scanning electricity
Mirror figure (Fig. 3 (a)) and transmission electron microscope picture (Fig. 3 (b)).
Fig. 4 is the gained negative material (Fe of the embodiment of the present invention 12O3@C) cycle performance in lithium ion battery.
Fig. 5 is the gained nitrogen-doped carbon of the embodiment of the present invention 2 cladding di-iron trioxide negative material (Fe2O3@C) scanning electricity
Mirror figure (Fig. 5 (a)) and transmission electron microscope picture (Fig. 5 (b)).
Fig. 6 is the gained negative material (Fe of the embodiment of the present invention 22O3@C) cycle performance in lithium ion battery.
Specific embodiment
Embodiments of the invention are elaborated below, following embodiments are entered under premised on technical solution of the present invention
Row is implemented, and gives detailed implementation method and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Experimental technique used in following embodiments is conventional method unless otherwise specified.
Agents useful for same, material etc. unless otherwise specified, are commercially obtained in following embodiments.
Battery performance test, using blue electricity battery test system, is by following embodiments in following embodiments
Fe2O3@C negative materials, Ketjen black and Kynoar (pVDF) are 8 according to mass ratio:1:1 well mixed is dissolved in nmp solution
In be made slurries, be equably applied on copper current collector (Copper Foil) and be made working electrode, with glass fibre membrane as barrier film, electrolyte choosing
It is 1M lithium hexafluoro phosphates (LiPF with concentration6) ethylene carbonate (EC)/dimethyl carbonate (DEC) mixed solution (volume ratio is
1:1) 2032 button cells, are assembled into full of argon gas glove box, test voltage scope is 0.01V~3V (vs Li+/Li)。
Embodiment 1
The present embodiment prepares nitrogen-doped carbon cladding di-iron trioxide lithium ion battery negative material as follows：
A, Iron(III) chloride hexahydrate and two hypophosphite monohydrate sodium dihydrogens add 300mL water, obtain reaction solution；In reaction solution
The concentration of middle ferric trichloride is 0.02mol/L, the concentration of sodium dihydrogen phosphate is 0.45mmol/L；
By in reaction solution addition reactor, 105 DEG C of hydro-thermal reaction 48h after naturally cooling to room temperature, are centrifuged, wash, that is, obtain
Obtain nanometer fusiformis di-iron trioxide.
B, 50mg nanometers of fusiformis di-iron trioxide is dispersed in 200mL by isopropyl alcohol and water by volume 4:1 constitute it is mixed
Close in liquid, then ultrasonic agitation 30min adds 2mL ammoniacal liquor and 0.2mL tetraethyl orthosilicates under agitation, continue to stir
4h, centrifugation, washing, that is, obtain fusiformis presoma Fe2O3@SiO2；
C, the fusiformis presoma Fe for being obtained step B2O3@SiO2It is dispersed in 100mL ethanol, is subsequently adding 3.2g's
PVP, stirs 18h, and centrifugation, washing complete high molecular surfactant modification；
Fusiformis presoma Fe after modifying2O3@SiO2It is scattered in 25mL deionized waters, is subsequently adding 0.2mL pyrroles's list
Body, ultrasonic 30min, then the liquor ferri trichloridi that 25mL concentration is 17.8mmol/L is added dropwise under agitation, finally gather
Reaction 4h is closed, is centrifuged, washs, dried, that is, obtain Fe2O3@SiO2@Ppy；
D, by Fe2O3@SiO2@Ppy are placed in argon atmosphere, and 600 DEG C, annealing are warming up to the heating rate of 3 DEG C/min
4h, makes polypyrrole be carbonized, and obtains Fe2O3@SiO2@C；
E, by Fe2O3@SiO2@C are performed etching in being put into 2M sodium hydroxide solutions, to remove SiO2, that is, obtain and carry interlayer
The nitrogen-doped carbon cladding di-iron trioxide negative material Fe of gap structure2O3@C。
Fig. 1 is the present embodiment gained nanometer fusiformis di-iron trioxide Fe2O3(Fig. 1 (a)) and the oxidation two of nitrogen-doped carbon cladding three
Iron negative material (Fe2O3@C) (Fig. 1 (b)) optical photograph.
Fig. 2 is the present embodiment gained nanometer fusiformis di-iron trioxide Fe2O3Scanning electron microscope (SEM) photograph (Fig. 2 (a)) and transmission electron microscope
Figure (Fig. 2 (b)), as can be seen from the figure product morphology is uniform, and axial length~550nm long, short axle be long~85nm.
Fig. 3 is embodiment of the present invention gained nitrogen-doped carbon cladding di-iron trioxide negative material (Fe2O3@C) ESEM
Figure (Fig. 3 (a)) and transmission electron microscope picture (Fig. 3 (b)).Understand the interlayer gap structure thickness~20nm of material, nitrogen-doped carbon thickness~
30nm, final structure is remained intact, and, without breakage, in charge and discharge process, the presence of complete carbon shell can be effectively for exterior carbon shell
The reunion and efflorescence of di-iron trioxide are prevented, therefore negative material can have good cyclical stability.
According to anode coat, lithium piece, barrier film, electrolyte, negative pole, pad, reed, positive pole shell order assembled battery,
Carry out performance test.Fig. 4 is the present embodiment negative material (Fe2O3@C) cycle performance in lithium ion battery, its test multiplying power
It is 0.1C, it can be seen that material first circle specific discharge capacity is 1874mA h g-1, 1312mA h g are still kept after the circle of circulation 200-1
Reversible specific capacity, show Fe2O3@C have good cycle performance.
Embodiment 2
The present embodiment prepares nitrogen-doped carbon cladding di-iron trioxide lithium ion battery negative material as follows：
A, Iron(III) chloride hexahydrate and two hypophosphite monohydrate sodium dihydrogens add 300mL water, obtain reaction solution；In reaction solution
The concentration of middle ferric trichloride is 0.02mol/L, the concentration of sodium dihydrogen phosphate is 0.45mmol/L；
By in reaction solution addition reactor, 105 DEG C of hydro-thermal reaction 48h after naturally cooling to room temperature, are centrifuged, wash, that is, obtain
Obtain nanometer fusiformis di-iron trioxide.
B, 50mg nanometers of fusiformis di-iron trioxide is dispersed in 200mL by isopropyl alcohol and water by volume 4:1 constitute it is mixed
Close in liquid, then ultrasonic agitation 30min adds 2mL ammoniacal liquor and 0.3mL tetraethyl orthosilicates under agitation, continue to stir
4h, centrifugation, washing, that is, obtain fusiformis presoma Fe2O3@SiO2；
C, the fusiformis presoma Fe for being obtained step B2O3@SiO2It is dispersed in 100mL ethanol, is subsequently adding 3.2g's
PVP, stirs 18h, and centrifugation, washing complete high molecular surfactant modification；
Fusiformis presoma Fe after modifying2O3@SiO2It is scattered in 25mL deionized waters, is subsequently adding 0.3mL pyrroles's list
Body, ultrasonic 30min, then the liquor ferri trichloridi that 25mL concentration is 26.6mmol/L is added dropwise under agitation, finally gather
Reaction 4h is closed, is centrifuged, washs, dried, that is, obtain Fe2O3@SiO2@Ppy；
D, by Fe2O3@SiO2@Ppy are placed in argon atmosphere, and 600 DEG C, annealing are warming up to the heating rate of 3 DEG C/min
4h, makes polypyrrole be carbonized, and obtains Fe2O3@SiO2@C；
E, by Fe2O3@SiO2@C are performed etching in being put into 2M sodium hydroxide solutions, to remove SiO2, that is, obtain and carry interlayer
The nitrogen-doped carbon cladding di-iron trioxide negative material Fe of gap structure2O3@C。
Fig. 5 is embodiment of the present invention gained nitrogen-doped carbon cladding di-iron trioxide negative material (Fe2O3@C) ESEM
Figure (Fig. 5 (a)) and transmission electron microscope picture (Fig. 5 (b)).Understand the interlayer gap structure thickness~30nm of material, nitrogen-doped carbon thickness~
30nm, final structure is remained intact, and exterior carbon shell protects the di-iron trioxide of inside, therefore negative pole material well without breakage
Material has good cyclical stability.
According to anode coat, lithium piece, barrier film, electrolyte, negative pole, pad, reed, positive pole shell order assembled battery,
Carry out performance test.Fig. 6 is the present embodiment negative material (Fe2O3@C) cycle performance in lithium ion battery, its test multiplying power
It is 0.1C, it can be seen that material first circle specific discharge capacity is 1420mA h g-1, 1051mA h g are still kept after the circle of circulation 200-1
Reversible specific capacity, show Fe2O3@C have good cycle performance.
Exemplary embodiment of the invention is the foregoing is only, is not intended to limit the invention, it is all of the invention
Any modification, equivalent and improvement made within spirit and principle etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of lithium ion battery coats di-iron trioxide negative material with nitrogen-doped carbon, it is characterised in that：It is in nanometer fusiformis
As presoma after the outer surface coated silica layer of di-iron trioxide, then one layer of conduction is coated in silicon dioxide layer outer surface
Polypyrrole, it is finally annealed to make polypyrrole carbonization, etched removal silica interlayer, that is, obtain with interlayer gap structure
Nitrogen-doped carbon coats di-iron trioxide negative material.
2. lithium ion battery according to claim 1 coats di-iron trioxide negative material with nitrogen-doped carbon, and its feature exists
In：100~the 3000nm of axial length long of the nanometer fusiformis di-iron trioxide, short axle 50~1800nm long, interlayer gap structure thickness 5
~30nm, N doping carbon-coating is the amorphous graphite of 20~35nm of thickness；Di-iron trioxide negative pole material is coated in the nitrogen-doped carbon
The weight/mass percentage composition of nitrogen-doped carbon is 34%~45% in material.
3. the lithium ion battery described in a kind of claim 1 or 2 coats the preparation of di-iron trioxide negative material with nitrogen-doped carbon
Method, it is characterised in that comprise the following steps：
A, by solvent thermal reaction synthesize nanometer fusiformis di-iron trioxide；
B, in the basic conditions, titanium dioxide is coated by sol-gel process in the outer surface of the nanometer fusiformis di-iron trioxide
Silicon layer, obtains fusiformis presoma Fe2O3@SiO2；
C, the fusiformis presoma Fe is modified with high molecular surfactant2O3@SiO2, then add pyrrole monomer and initiation
Agent is reacted, and makes fusiformis presoma Fe after modification2O3@SiO2Outer surface coats one layer of electric polypyrrole, obtains Fe2O3@SiO2@
Ppy；
D, under atmosphere of inert gases to the Fe2O3@SiO2@Ppy are made annealing treatment, and polypyrrole is carbonized, and obtain Fe2O3@
SiO2@C；
E, by the Fe2O3@SiO2@C are performed etching in being put into alkaline solution, to remove SiO2, that is, obtain with interlayer space knot
The nitrogen-doped carbon cladding di-iron trioxide negative material Fe of structure2O3@C。
4. preparation method according to claim 3, it is characterised in that specifically carry out as follows：
A, by solvent thermal reaction synthesize nanometer fusiformis di-iron trioxide；
B, 50mg nanometers of fusiformis di-iron trioxide is dispersed in 100mL~200mL by isopropyl alcohol and water by volume 4:1 composition
In mixed liquor, then 10~60min of ultrasonic agitation adds 1~5mL ammoniacal liquor and the positive silicic acid of 0.1mL~0.6mL under agitation
Tetra-ethyl ester, continues to stir 4~24h, and centrifugation, washing obtain fusiformis presoma Fe2O3@SiO2；
C, the fusiformis presoma Fe for being obtained step B2O3@SiO2It is dispersed in 100mL ethanol, is subsequently adding 0.5g~3.2g
High molecular surfactant, stirs 12~48h, and centrifugation, washing complete high molecular surfactant modification；
Fusiformis presoma Fe after modifying2O3@SiO2It is scattered in 25mL deionized waters, is subsequently adding 0.18~0.3mL pyrroles's lists
Body, ultrasonic 30min, then the initiator solution that 25mL concentration is 15~27mmol/L is added dropwise under agitation, finally gather
4~12h of reaction is closed, is centrifuged, washs, dried, that is, obtain Fe2O3@SiO2@Ppy；
D, by the Fe2O3@SiO2@Ppy are placed in atmosphere of inert gases, and 550 are warming up to the heating rate of 2 DEG C -5 DEG C/min
DEG C -650 DEG C, anneal 2~4h, polypyrrole is carbonized, and obtains Fe2O3@SiO2@C；
E, by the Fe2O3@SiO2@C are performed etching in being put into alkaline solution, to remove SiO2, that is, obtain with interlayer space knot
The nitrogen-doped carbon cladding di-iron trioxide negative material Fe of structure2O3@C。
5. the preparation method according to claim 3 or 4, it is characterised in that the nanometer fusiformis di-iron trioxide is by as follows
It is prepared by method：
By in the mixed liquor of ferric trichloride and sodium dihydrogen phosphate or sodium hypophosphite addition water and ethanol, reaction solution is obtained；Institute
The concentration of ferric trichloride in reaction solution is stated for 0.015~0.02mol/L, the concentration of sodium dihydrogen phosphate or sodium hypophosphite is 0.1
~0.5mmol/L；In the mixed liquor of water and ethanol, the percentage by volume of ethanol is 0-50%；
By the reaction solution add reactor in, 98~105 DEG C of 48~168h of hydro-thermal reaction, after being then so cooled to room temperature, from
The heart, washing, that is, obtain nanometer fusiformis di-iron trioxide.
6. the preparation method according to claim 3 or 4, it is characterised in that：The high molecular surfactant is polyethylene
At least one in pyrrolidones, poly amic acid, hydroxyethyl cellulose and polyoxyethylene analog copolymer.
7. the preparation method according to claim 3 or 4, it is characterised in that：The initiator is ammonium persulfate, tri-chlorination
At least one in iron, hydrogen peroxide, potassium bichromate and Potassiumiodate.
8. the preparation method according to claim 3 or 4, it is characterised in that：Alkaline solution described in step E is NaOH
Solution or potassium hydroxide solution.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107742700A (en) * | 2017-09-15 | 2018-02-27 | 苏州思创源博电子科技有限公司 | A kind of preparation method of carbon coating titanium lithium composite negative pole material |
| CN107978750A (en) * | 2017-11-27 | 2018-05-01 | 江西师范大学 | The forming method of anode material of lithium-ion battery |
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| CN108807987A (en) * | 2018-07-07 | 2018-11-13 | 苏州思创源博电子科技有限公司 | A kind of preparation method of carbon coating selenizing tin negative pole material |
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| CN108899489A (en) * | 2018-06-19 | 2018-11-27 | 苏州思创源博电子科技有限公司 | A kind of preparation method of carbon coating lithium iron oxide cell negative electrode material |
| CN108899491A (en) * | 2018-06-19 | 2018-11-27 | 苏州思创源博电子科技有限公司 | A kind of lithium battery aoxidizes the preparation method of tin negative pole material with carbon coating |
| CN109192932A (en) * | 2018-07-12 | 2019-01-11 | 苏州思创源博电子科技有限公司 | A kind of preparation method of carbon titanium composite lithium ion battery negative electrode material |
| CN113490403A (en) * | 2021-05-12 | 2021-10-08 | 南昌航空大学 | Preparation method of alpha-Fe 2O3 doped silica nanoparticle wave-absorbing material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492576A (en) * | 2008-01-22 | 2009-07-29 | 中国科学院化学研究所 | Carbon nano-complex particle, preparation and uses thereof |
| CN105470483A (en) * | 2015-12-04 | 2016-04-06 | 齐鲁工业大学 | Preparation method of anode material N-doped carbon-coated cobaltous oxide nanotube for lithium-ion battery |
| CN105664936A (en) * | 2016-01-07 | 2016-06-15 | 上海工程技术大学 | Method for preparing nano composite material having core-shell structure with dopamine as carbon source |
| CN106450251A (en) * | 2016-12-23 | 2017-02-22 | 合肥工业大学 | Anode material for Li-ion batteries and preparation method thereof |
-
2017
- 2017-03-09 CN CN201710137659.5A patent/CN106816595B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492576A (en) * | 2008-01-22 | 2009-07-29 | 中国科学院化学研究所 | Carbon nano-complex particle, preparation and uses thereof |
| CN105470483A (en) * | 2015-12-04 | 2016-04-06 | 齐鲁工业大学 | Preparation method of anode material N-doped carbon-coated cobaltous oxide nanotube for lithium-ion battery |
| CN105664936A (en) * | 2016-01-07 | 2016-06-15 | 上海工程技术大学 | Method for preparing nano composite material having core-shell structure with dopamine as carbon source |
| CN106450251A (en) * | 2016-12-23 | 2017-02-22 | 合肥工业大学 | Anode material for Li-ion batteries and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIN LIANG: "Porous r-Fe2O3 spheres coated with N-doped carbon from polydopamine as Li-ion battery anode materials", 《NANOTECHNOLOGY》 * |
| 张鑫: "Fe2O3@SiO2 椭球粒子的制备、自组装及其光学性能研究", 《中国博士学位论文全文数据库(电子期刊)》 * |
Cited By (13)
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| CN107978750B (en) * | 2017-11-27 | 2020-07-24 | 江西师范大学 | Method for forming negative electrode material of sodium ion battery |
| CN107978750A (en) * | 2017-11-27 | 2018-05-01 | 江西师范大学 | The forming method of anode material of lithium-ion battery |
| CN108400293A (en) * | 2018-01-26 | 2018-08-14 | 合肥国轩高科动力能源有限公司 | Nitrogen-doped carbon-coated silicon nanomaterial and preparation method and application thereof |
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