CN109950477A - A kind of modified method in water system ion battery electrode materials surface - Google Patents
A kind of modified method in water system ion battery electrode materials surface Download PDFInfo
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- CN109950477A CN109950477A CN201711379570.6A CN201711379570A CN109950477A CN 109950477 A CN109950477 A CN 109950477A CN 201711379570 A CN201711379570 A CN 201711379570A CN 109950477 A CN109950477 A CN 109950477A
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- 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
Abstract
The invention belongs to new energy materials and electrochemical energy source fields, are related to a kind of method for improving water system ion battery electrode materials performance.The surface modifying method is the following steps are included: certain proportion modifying agent and positive electrode or negative electrode material are mixed；Solvent is added, stirs evenly；Ball milling；It is dry；Obtained mixture is heated into the regular hour in certain atmosphere；Crushing obtains modified electrode material.The modified electrode material is micro Nano material.Method provided by the invention is low for equipment requirements, and synthesis cost is cheap.The electrode material of the method synthesis provided through the invention has excellent processing performance, electric conductivity increases, be conducive to the infiltration of water system ion, it can make the performance capacity that active material is bigger, so as to make up volume change and bring energy density reduces, the chemical property of material is effectively improved.
Description
Technical field
The invention belongs to new energy materials and electrochemical energy source fields, are related to a kind of improvement water system ion battery electrode material
Expect the method for performance.
Background technique
Due to the environmental problem that fossil energy is non-renewable and its generates, so that people start attention green energy resource and can be again
The research and development and application of the raw energy.In recent years, as renewable energy (such as solar battery array and wind power plant) is in the whole world
The rapid proliferation of energy market, a significant challenge for needing to overcome are the safe and cost-effective electric power storage systems of exploitation, with
Just intermittent renewable energy is preferably utilized.
From traditional lead-acid battery to advanced lithium ion battery, various types of battery chemistries have been proposed as one kind
The energy storage strategy of possible power grid scale；However, these batteries otherwise limited by cost and resource or be due to
Their running durability and safety deficiency causes extensive energy storage not to be applied slowly.Water system battery has safety collar
The advantages that protecting, is cheap, cycle performance is excellent, becomes the energy-storage battery for most possibly realizing extensive energy storage.
Electrode material is an important factor for restricting water system ion battery.Some materials used at present due to its electric conductivity compared with
Difference and volume changes energy density is caused to reduce in charge and discharge process, so that its cycle performance reduces.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of modified methods in water system ion battery electrode materials surface, should
Method is low for equipment requirements, and synthesis cost is cheap.The electrode material of the method synthesis provided through the invention has excellent add
Work performance, electric conductivity increase, are conducive to the infiltration of water system ion, can make the performance capacity that active material is bigger, so as to
It makes up volume change and bring energy density reduces, effectively improves the chemical property of material.
The present invention relates to a kind of modified methods in water system ion battery electrode materials surface.The surface modifying method include with
Lower step: certain proportion modifying agent and positive electrode or negative electrode material are mixed；It stirs evenly；Ball milling；It is dry；It is mixed by what is obtained
It closes object and heats the regular hour in certain atmosphere；Crushing obtains modified electrode material.
Modified electrode material is micro Nano material through the invention.
The modified method in water system ion battery electrode materials surface of the invention, which is characterized in that the method includes with
Lower step:
Certain proportion modified material and positive electrode or negative electrode material are mixed；
Solvent is added, stirs evenly；
Ball milling；
It is dry；
Obtained mixture is heated into the regular hour in certain atmosphere；
Crushing obtains modified electrode material.
Above-mentioned uniform hybrid mode is mechanical stirring, air-flow mixing, grinding wherein at least one.
Above-mentioned modified material is carbonaceous material, nitrogenous material, contains boron material, phosphorated material, metal material wherein at least one
Kind.
Above-mentioned modified material and positive electrode or the mass ratio of negative electrode material are (0.5-15): (99.5-85).
Above-mentioned carbonaceous material is graphite, carbon black, active carbon, carbon nanotube, carbon fiber, carbon ball, graphene, porous carbon
Material, charcoal-aero gel, template carbon, Carbide-derived carbons, C-base composte material, glucose, sucrose, fructose, maltose, starch, fibre
Dimension element, furfuryl alcohol wherein at least one.
Above-mentioned nitrogenous material is urea, ammonium hydroxide, acetoxime, aniline, polyaniline, methylamine, alkylammonium salt wherein at least one.
The above-mentioned boron material that contains is boric acid, phenyl boric acid, trimethylborate wherein at least one.
Above-mentioned phosphorated material be triphenyl phosphorus, sodium dihydrogen phosphate, a hypophosphite monohydrate sodium dihydrogen, sodium dihydrogen phosphate dihydrate,
Disodium hydrogen phosphate, sodium phosphate, sodium pyrophosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, phosphoric acid wherein at least one.
Above-mentioned metal material is zinc, manganese, cobalt, iron, nickel, vanadium, silver, rare earth metal wherein at least one.
Above-mentioned solvent be added be deionized water, tap water, ethyl alcohol, ethylene glycol, propyl alcohol, isopropanol, acetone wherein extremely
Few one kind.
Above-mentioned ball milling work step is to use agitating ball mill with 300-1200r/min ball milling 0.5-12h.
Above-mentioned drying work step drying temperature is 60-250 DEG C, and drying means is to spontaneously dry, be dried in vacuo, is spraying dry
Dry, heated-air drying wherein at least one.
Above-mentioned heating atmosphere is nitrogen, ammonia, argon gas, helium, neon, hydrogen, carbon dioxide wherein at least one, is risen
Warm rate is 1 DEG C/min-20 DEG C/min, and heating temperature is 600 DEG C -1200 DEG C, heating time 0.5h-12h.
Detailed description of the invention
Fig. 1 is the MnO prepared in the embodiment of the present invention 12The constant current charge-discharge curve graph of/C.
Fig. 2 is the NaTi prepared in the embodiment of the present invention 22(PO4)3Scanning electron microscope (SEM) figure of/C.
Fig. 3 is the NaTi prepared in the embodiment of the present invention 22(PO4)3The constant current charge-discharge curve graph of/C.
Fig. 4 is the NaTi prepared in the embodiment of the present invention 32(PO4)3The constant current charge-discharge curve graph of/Zn.
Fig. 5 is the MnO prepared in the embodiment of the present invention 1 and comparative example 12/ C and MnO2Cycle performance figure.
Fig. 6 is MnO in comparative example 1 of the present invention2Constant current charge-discharge curve graph.
Specific embodiment
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, but protection of the invention
Range is not limited thereto.
Embodiment 1
Manganese dioxide and sucrose are uniformly mixed according to mass ratio 95:5, a certain amount of ethyl alcohol is added, then with
The speed ball milling 2h of 800r/min.80 DEG C of dry 12h in drying box are subsequently placed in, obtained solid is put into argon in atmosphere furnace
900 DEG C of heating 3h in compression ring border crush it with mortar to obtain modified electrode material MnO after cooling2/C。
The MnO prepared with example 12/ C, conductive black and binder Kynoar are mixed according to mass ratio 80:10:10,
It is sized mixing with N-Methyl pyrrolidone, is then coated on the graphite paper handled well, it is 12 hours dry.Then with 1M aqueous sodium sulfate
Liquid is electrolyte, and absorbent charcoal material is that cathode carries out constant current charge-discharge and cycle performance test, and charging and discharging currents density is 0.1A/
g.Fig. 1 is modified MnO2The constant current charge-discharge curve graph of/C.
Embodiment 2
Titanium phosphate sodium and graphite are uniformly mixed according to mass ratio 90:10, a certain amount of ethyl alcohol is added, then with 800r/
The speed ball milling 2h of min.80 DEG C of dry 12h in drying box are subsequently placed in, obtained solid is put into atmosphere furnace in ar gas environment
900 DEG C of heating 3h crush it with mortar to obtain modified electrode material NaTi after cooling2(PO4)3/C。
The NaTi prepared with example 22(PO4)3/ C, conductive black and binder Kynoar are according to mass ratio 80:10:
10 mixing, are sized mixing with N-Methyl pyrrolidone, are then coated on the graphite paper handled well, 12 hours dry.Then with 1M sulphur
Acid sodium aqueous solution is electrolyte, and absorbent charcoal material is that cathode carries out constant current charge-discharge and cycle performance test, and charging and discharging currents are close
Degree is 0.05A/g.Fig. 2 and Fig. 3 is the constant current charge-discharge curve graph and constant current charge-discharge cycle performance song of the material respectively
Line chart.
Embodiment 3
Titanium phosphate sodium and zinc powder are uniformly mixed according to mass ratio 95:5, a certain amount of isopropanol is added, then with 600r/
The speed ball milling 2h of min.80 DEG C of dry 12h in vacuum oven are subsequently placed in, it is crushed to obtain modified electricity with mortar
Pole material NaTi2(PO4)3/Zn。
The NaTi prepared with example 32(PO4)3/ Zn, conductive black and binder Kynoar are according to mass ratio 80:10:
10 mixing, are sized mixing with N-Methyl pyrrolidone, are then coated on the graphite paper handled well, 12 hours dry.Then with 1M sulphur
Acid sodium aqueous solution is electrolyte, and absorbent charcoal material is that cathode carries out constant current charge-discharge test, and charging and discharging currents density is 0.2A/g.
Fig. 4 is the constant current charge-discharge curve graph of the positive electrode.
Comparative example 1
With the MnO modified without surface2, conductive black and binder Kynoar it is mixed according to mass ratio 80:10:10
It closes, is sized mixing with N-Methyl pyrrolidone, be then coated on the graphite paper handled well, it is 12 hours dry.Then with 1M sodium sulphate
Aqueous solution is electrolyte, and absorbent charcoal material is that cathode carries out constant current charge-discharge test, and charging and discharging currents density is 0.1A/g.Fig. 5
Be by the method for modifying before modified after material cycle performance figure.Fig. 6 is MnO2Constant current charge-discharge curve graph.
Embodiment of above is only for interpreting the claims, and protection scope of the present invention is not limited to specification.
Anyone skilled in the art within the technical scope of the present disclosure, the variation that can readily occur in or replaces
It changes, is included within the scope of the present invention.
Claims (14)
1. a kind of modified method in water system ion battery electrode materials surface, which is characterized in that the method for modifying includes following
Step: certain proportion modified material and positive electrode or negative electrode material are mixed；Solvent is added, stirs evenly；Ball milling；It is dry；
Obtained mixture is heated into the regular hour in certain atmosphere；Crushing obtains modified electrode material.
2. the modified method in water system ion battery electrode materials according to claim 1 surface, which is characterized in that modified
Material be nanometer or micro materials.
3. the modified method in water system ion battery electrode materials according to claim 1 surface, which is characterized in that it passes through
Mechanical stirring, air-flow mixing, grinding wherein at least one mix modified material and positive electrode or negative electrode material.
4. the method modified with electrode material surface as claimed in claim 3 according to claim 1, it is characterised in that: described to change
Property material and positive electrode or the mass ratio of negative electrode material be (0.5-15): (99.5-85).
5. the method modified with electrode material surface as claimed in claim 3 according to claim 1, it is characterised in that: described to change
Property material be carbonaceous material, nitrogenous material, contain boron material, phosphorated material, metal material wherein at least one.
6. the method modified with the electrode material surface described in claim 5 according to claim 1, it is characterised in that: described to contain
Carbon material is graphite, carbon black, active carbon, carbon nanotube, carbon fiber, carbon ball, graphene, porous carbon material, charcoal-aero gel, template
Charcoal, Carbide-derived carbons, C-base composte material, glucose, sucrose, fructose, maltose, starch, cellulose, furfuryl alcohol are wherein at least
It is a kind of.
7. the method modified with the electrode material surface described in claim 5 according to claim 1, it is characterised in that: described to contain
Nitrogen material is urea, ammonium hydroxide, acetoxime, aniline, polyaniline, methylamine, alkylammonium salt wherein at least one.
8. the method modified with the electrode material surface described in claim 5 according to claim 1, it is characterised in that: described to contain
Boron material is boric acid, phenyl boric acid, trimethylborate wherein at least one.
9. the method modified with the electrode material surface described in claim 5 according to claim 1, it is characterised in that: described to contain
Phosphate material is triphenyl phosphorus, sodium dihydrogen phosphate, a hypophosphite monohydrate sodium dihydrogen, sodium dihydrogen phosphate dihydrate, disodium hydrogen phosphate, phosphoric acid
Sodium, sodium pyrophosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, phosphoric acid wherein at least one.
10. the method modified with the electrode material surface described in claim 5 according to claim 1, it is characterised in that: the gold
Category material is zinc, manganese, cobalt, iron, nickel, vanadium, silver, rare earth metal wherein at least one.
11. the modified method of electrode material surface according to claim 1, which is characterized in that the solvent of addition be go from
Sub- water, tap water, ethyl alcohol, ethylene glycol, propyl alcohol, isopropanol, acetone it is one or more.
12. the modified method of electrode material surface according to claim 1, it is characterised in that: the ball milling work step is
Use agitating ball mill with 300-1200r/min ball milling 0.5-12h.
13. the modified method of electrode material surface according to claim 1, it is characterised in that: the drying work step is dry
Dry temperature is 60-250 DEG C, and drying means is to spontaneously dry, vacuum drying, be spray-dried, heated-air drying wherein at least one.
14. the modified method of electrode material surface according to claim 1, it is characterised in that: the heating atmosphere is
Nitrogen, ammonia, argon gas, helium, neon, hydrogen, carbon dioxide wherein at least one, heating rate be 1 DEG C/min-20 DEG C/
Min, heating temperature are 600 DEG C -1200 DEG C, heating time 0.5h-12h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112864388A (en) * | 2021-01-26 | 2021-05-28 | 广州倬粤电能科技有限公司 | Water-based zinc ion soft package battery and preparation method thereof |
| CN115312968A (en) * | 2022-09-09 | 2022-11-08 | 盐城师范学院 | Lithium ion battery based on high-temperature-resistant diaphragm and preparation method thereof |
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| US20040157126A1 (en) * | 2002-11-04 | 2004-08-12 | Ilias Belharouak | Positive electrode material for lithium ion batteries |
| US20090305135A1 (en) * | 2008-06-04 | 2009-12-10 | Jinjun Shi | Conductive nanocomposite-based electrodes for lithium batteries |
| CN103441259A (en) * | 2013-08-12 | 2013-12-11 | 恩力能源科技（南通）有限公司 | Anode material of high-magnification aqueous alkali metal electrochemical battery and preparation method of anode material |
| CN103606654A (en) * | 2012-12-21 | 2014-02-26 | 燕山大学 | Method for preparing carbon-coated manganite composite material |
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Patent Citations (5)
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| US20040157126A1 (en) * | 2002-11-04 | 2004-08-12 | Ilias Belharouak | Positive electrode material for lithium ion batteries |
| US20090305135A1 (en) * | 2008-06-04 | 2009-12-10 | Jinjun Shi | Conductive nanocomposite-based electrodes for lithium batteries |
| CN103606654A (en) * | 2012-12-21 | 2014-02-26 | 燕山大学 | Method for preparing carbon-coated manganite composite material |
| CN103441259A (en) * | 2013-08-12 | 2013-12-11 | 恩力能源科技（南通）有限公司 | Anode material of high-magnification aqueous alkali metal electrochemical battery and preparation method of anode material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112864388A (en) * | 2021-01-26 | 2021-05-28 | 广州倬粤电能科技有限公司 | Water-based zinc ion soft package battery and preparation method thereof |
| CN115312968A (en) * | 2022-09-09 | 2022-11-08 | 盐城师范学院 | Lithium ion battery based on high-temperature-resistant diaphragm and preparation method thereof |
| CN115312968B (en) * | 2022-09-09 | 2023-12-22 | 盐城师范学院 | Lithium ion battery based on high-temperature-resistant diaphragm and preparation method thereof |
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