CN107086300B - It is a kind of for the negative electrode material of sodium-ion battery and its preparation and application - Google Patents
It is a kind of for the negative electrode material of sodium-ion battery and its preparation and application Download PDFInfo
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- CN107086300B CN107086300B CN201710261280.5A CN201710261280A CN107086300B CN 107086300 B CN107086300 B CN 107086300B CN 201710261280 A CN201710261280 A CN 201710261280A CN 107086300 B CN107086300 B CN 107086300B
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- nickel
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- ion battery
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- negative electrode
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 33
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 25
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- BXNRPWOFOQNQDE-UHFFFAOYSA-N boric acid;nickel Chemical compound [Ni].OB(O)O BXNRPWOFOQNQDE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000004781 supercooling Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 9
- 229910052708 sodium Inorganic materials 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- HKFZDVPCCOOGEV-UHFFFAOYSA-N nickel(3+);borate Chemical compound [Ni+3].[O-]B([O-])[O-] HKFZDVPCCOOGEV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000010792 warming Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- -1 oxo transition metal Chemical class 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910004591 Na2FePO4F Inorganic materials 0.000 description 1
- 229910018970 NaNi0.5Mn0.5O2 Inorganic materials 0.000 description 1
- 229910001222 NaVPO4F Inorganic materials 0.000 description 1
- 229910019850 NaxCoO2 Inorganic materials 0.000 description 1
- 229910019898 NaxMnO2 Inorganic materials 0.000 description 1
- 229910006913 SnSb Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000035922 thirst Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of negative electrode material for sodium-ion battery, chemical formula Ni3B2O6, crystal structure is orthorhombic structure, belongs to Pnnm space group.It the present invention also provides the preparation method of the above-mentioned negative electrode material for sodium-ion battery, after mixing by nickel source and boron source, is sintered under the conditions of oxidizing atmosphere, then through supercooling, pure phase boric acid nickel material is made in washing, baking step.The present invention has that raw material sources are wide, preparation cost is low, preparation process flow is simple, and low to the performance requirement of equipment, product purity is high, the features such as having a safety feature.When boric acid nickel material obtained is applied to sodium-ion battery, good storage sodium ability and excellent chemical property are shown.
Description
Technical field
The invention belongs to materialogy fields, are related to a kind of energy storage material, specifically a kind of for sodium-ion battery
Negative electrode material and its preparation and application.
Background technique
The fast development of the environmentally protective energy such as solar energy, wind energy, tide energy proposes higher for its mating energy-storage system
Requirement and broader practice range.As the energy-storage system for most having application prospect, the research and development of electrochmical power source is focused
The attention of numerous scholars.Since the commercialization of the lithium ion battery nineties in last century, due to close with high voltage, high-energy
The advantages such as degree, memory-less effect and be rapidly developed, be widely used to now portable electronic device, electric car etc. side
Face；But due to being limited by lithium resource, people are studying the chemical cell system of alternative lithium ion battery energetically.In
In the periodic table of elements, sodium element and elemental lithium are in the adjacent periods of same main group, have similar physics and chemical property；This
Outside, sodium is compared with lithium, and because its reserves is richer, refinement is simpler, is distributed the features such as more extensive and has unique advantage.Cause
This, sodium-ion battery can be used as a kind of electrochmical power source applied to extensive energy storage.
Sodium-ion battery has similar working principle with lithium ion battery, but since sodium ion has more than lithium ion
Big ionic radius and relative difficulty carry out reversible deintercalation in electrode material, and during embedding entry/exit, easily make material knot
Structure damage, makes battery capacity be lower, and cycle performance is deteriorated.Therefore the exploratory development of the novel electrode material haveing excellent performance is sodium
The key subject of ion battery research and development.Currently, such as oxo transition metal containing sodium is concentrated in the research of sodium-ion battery positive material
Compound (such as NaxCoO2、NaxMnO2) and transition metal fluorophosphoric acid sodium salt (such as NaVPO4F、Na2FePO4F) etc..And in cathode
Research in terms of material is relatively fewer.
It,, cannot since sodium ion radius is larger in terms of Carbon Materials in research for the negative electrode material of sodium-ion battery
Carry out reversible deintercalation in traditional graphite as anode material for lithium-ion battery again, non-graphitic carbon material focuses primarily upon hard carbon and soft
Carbon.Komaba et al. improves the first charge discharge efficiency and stable circulation that hard carbon stores up sodium by improving the micro-structure of electrolyte and hard carbon
Property, it is up to 90% using the first all coulombic efficiencies of button cell, circulation still had 220mAh/g after 100 weeks, with NaNi0.5Mn0.5O2For
Anode building full battery show preferable cycle performance (Advanced Functional Materials. 2011,21,
3859).In alloy material, Xiao etc. is prepared for SnSb/C nano-complex using high-energy ball milling method, cyclic process for the first time
Reversible storage sodium capacity be 544mAh/g, be demonstrated by preferable cyclical stability and high rate performance, maintained after recycling within 50 weeks
435mAh/g(Journal of the Chemical Society chemical Communications, 2012,48,
3321).Such material have huge development potentiality, but its in charge and discharge process as electrode volume expansion caused by
The variation of electrode material structure can cause the decaying of battery capacity, to restrict its development.In addition, metal oxide, titanate,
Organic matter etc. also can be used as the negative electrode material for sodium-ion battery.
Higher and higher as the requirement of energy storage device to sodium-ion battery with the research and development of new energy, people thirst for
Develop high-energy-density, long circulation life and the sodium ion negative electrode material for preparing the features such as simple.
Summary of the invention
For above-mentioned technical problem in the prior art, the present invention provides a kind of negative electrode materials for sodium-ion battery
And its it prepares and applies.
The present invention provides a kind of negative electrode material for sodium-ion battery, chemical formula Ni3B2O6, crystal structure is
Orthorhombic structure belongs to Pnnm space group.
The present invention also provides the preparation methods of the above-mentioned negative electrode material for sodium-ion battery, weigh nickel source and boron
Source, any one or two kind of the nickel source in nickel oxide, nickel oxalate, nickel nitrate, nickel chloride or nickel sulfate and
Above combination, the boron source in diboron trioxide, boric acid, boron nitride, ammonium borate or phenyl boric acid any one or
The molar ratio of two kinds of person or more of combination, the nickel source and boron source is 3:2 ~ 3；After mixing, in oxidizing atmosphere item
It is sintered under part, the nickel source and boron source control heating rate during the sintering process as 1 ~ 20 DEG C/min；Sintering temperature is
500~1000℃；The sintered heat insulating time is 2-24h；Then it through supercooling, washs, drying is made for the negative of sodium-ion battery
Pole material boric acid nickel material.
Further, the nickel source and boron source are selected solution mixing, are stirred, the mixing side of wet ball grinding or dry ball milling
2 ~ 20h of one or more kinds of mixing of formula.
Further, the nickel source and boron source are sintered in air or oxygen.
The present invention also provides a kind of above-mentioned sodium-ion batteries, and by cathode, anode, electrolyte and diaphragm composition, described is negative
Pole material is the above-mentioned negative electrode material nickel borate for sodium-ion battery.
Further, above-mentioned a kind of sodium-ion battery, in 0.01V-3.0V (vs. Na+/ Na) charging/discharging voltage range
It is interior, there is 0.9 ~ 1.2V (vs. Na+/ Na) discharge voltage plateau, have greater than 500mAh/g initial reversible specific capacity.
Preferably, nickel source uses nickel oxide, nickel oxalate or nickel nitrate, and boron source uses diboron trioxide, boric acid or ammonium borate；
The molar ratio of nickel source and boron source is 3:2 ~ 2.5.4 ~ 8h is mixed using dry ball milling or wet ball grinding；Then it is burnt in air
Knot.
It is 1 ~ 20 DEG C/min that nickel source and boron source control heating rate during the sintering process as a preferred technical solution,；It burns
Junction temperature is 500 ~ 1000 DEG C；The sintered heat insulating time is 2 ~ 48h；Temperature is used to be washed for 40 ~ 100 DEG C of hot water；Drying
Temperature is 40 ~ 200 DEG C, and the time controls in 4 ~ 48h.More preferred, it is 2 ~ 10 DEG C/min that heating rate is controlled in sintering process；
Sintering temperature is 700 ~ 900 DEG C；The sintered heat insulating time be 3 ~ for 24 hours；Temperature is used to be washed for 60 ~ 100 DEG C of hot water；Drying
Temperature is 60 ~ 120 DEG C, and the time controls in 6 ~ 20h.
The present invention is compared with prior art, and technological progress is significant.The present invention provides one kind for sodium ion electricity
The application of the negative electrode material nickel borate in pond and preparation method thereof and nickel borate as the negative electrode material for sodium-ion battery.This
The boric acid nickel material of invention have raw material sources are wide, preparation cost is low, preparation process flow is simple, to the performance requirement of equipment
Low, product purity is high, the features such as having a safety feature.When boric acid nickel material obtained is applied to sodium-ion battery, show good
Storage sodium ability and excellent chemical property, be a kind of cathode material for sodium-ion battery with potential using value
Material.
Detailed description of the invention
Fig. 1 is the XRD spectrum for the boric acid nickel material that embodiment 2 is prepared；
Fig. 2 is the 1st time and the 2nd charging and discharging curve figure of the boric acid nickel material that embodiment 2 is prepared；
Fig. 3 is cycle performance figure of the boric acid nickel material that is prepared of embodiment 2 under 200mA/g current density.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Electrochemical property test:
Nickel borate negative electrode material, conductive carbon black and binder carboxymethyl cellulose (CMC) that the method for the present invention synthesizes are pressed
Mass ratio 80:10:10 is uniformly mixed, and is coated on copper foil, strikes out electrode slice after dry, for 24 hours in 100 DEG C of vacuum drying.
It is to electrode with metallic sodium；Mass ratio is dissolved in 1mol/L for ethylene carbonate (EC)/dimethyl carbonate of 1:1
(DMC) NaClO in mixed solution4Salting liquid is as electrolyte；Button cell is assembled into argon gas glove box.
Electrochemical property test is carried out using the blue electricity CT2001A type cell tester in Wuhan, charging/discharging voltage range is
0.01V~3.0V(vs. Na+/Na).Test temperature is 25 DEG C.
Embodiment 1
The nickel oxide of 2.25g is uniformly mixed with the boric acid of 1.488g by dry ball milling, in pipe under the conditions of air atmosphere
After being warming up to 650 DEG C and constant temperature holding 5h in formula furnace with 3 DEG C/min rate, cooled to room temperature is washed with 100 DEG C of hot water
Afterwards, 10h is dried at 100 DEG C dries obtained product nickel borate.
Embodiment 2
By the boric acid of the Nickelous nitrate hexahydrate of 8.73g and 1.488g by ball milling mixing it is uniform, under the conditions of air atmosphere
After being warming up to 850 DEG C and constant temperature holding 4h in tube furnace with 3 DEG C/min rate, cooled to room temperature is washed with 70 DEG C of hot water
Afterwards, 12h is dried at 120 DEG C to dry to obtain product nickel borate.
Fig. 1 is the XRD spectrum of boric acid nickel material, and the peak position of the XRD spectrum of material is entirely capable of and standard card (JCPDS.
No. 75-1809) on peak position and peak intensity match, illustrate that the ingredient of material obtained is Ni3B2O6, and deposited without miscellaneous phase
In.Fig. 2 is the 1st time and the 2nd charging and discharging curve figure of boric acid nickel material, as shown, the charging/discharging voltage model of 0.01-3.0V
In enclosing, in first time discharge process, there is an apparent discharge platform, and does not occur in second of discharge process identical
Platform illustrates that material structure evolution occurs during first charge-discharge.In charging process twice, two charging curve shape phases
Seemingly, there is not apparent charging voltage platform.Fig. 3 is circulation of the boric acid nickel material under 200mA/g charging and discharging currents density
Performance map, as shown, the 2nd discharge capacity is 494.7mA/g, the capacity of nickel borate is still kept after 60 circulations
292.8mAh/g illustrates that inventing the material has certain cycle performance and chemical property.
Embodiment 3
The boric acid of the nickel oxalate of 4.41g and 1.488g is uniform by ball milling mixing, with 5 DEG C/min under the conditions of air atmosphere
After rate is warming up to 750 DEG C and constant temperature 10h, cooled to room temperature after being washed with 80 DEG C of hot water, is dried 8h at 100 DEG C and is dried
It is dry to obtain product nickel borate.
Embodiment 4
The boric acid of the nickel sulfate of 7.89g and 1.488g is uniformly mixed by solution, dries 8h under the conditions of 90 DEG C
Presoma is made.It is naturally cold after presoma is warming up to 900 DEG C and constant temperature holding 15h under the conditions of air atmosphere with 8 DEG C/min rate
But to room temperature, after being washed with 80 DEG C of hot water, 9h is dried at 110 DEG C and dries to obtain product nickel borate.
Embodiment 5
The diboron trioxide of the nickel nitrate of 8.73g and 0.72g is uniform by ball milling mixing, with 5 under the conditions of air atmosphere
DEG C/after min rate is warming up to 900 DEG C and constant temperature 10h, cooled to room temperature is dried at 80 DEG C after being washed with 90 DEG C of hot water
15h dries to obtain product nickel borate.
Embodiment 6
The nickel oxalate of 4.41g is uniformly mixed with the diboron trioxide of 0.72g by wet ball grinding, under the conditions of air atmosphere
After being warming up to 700 DEG C and constant temperature 8h with 5 DEG C/min rate, cooled to room temperature, after being washed with 90 DEG C of hot water, at 120 DEG C
Drying 8h dries to obtain product nickel borate.
Embodiment 7
The diboron trioxide of the nickel sulfate of 7.89g and 0.72g is uniform by ball milling mixing, with 3 under the conditions of air atmosphere
DEG C/after min rate is warming up to 850 DEG C and constant temperature 15h, cooled to room temperature is dried at 100 DEG C after being washed with 80 DEG C of hot water
Dry 10h obtains product nickel borate.
Embodiment 8
The mixture of nickel oxide, the mixture of nickel nitrate and ammonium borate and phenyl boric acid is done by nickel boron molar ratio for 3:2.2
Method ball milling mixing 4h is sintered to uniform under air conditions, and it is 3 DEG C/min, sintering that heating rate is controlled in sintering process
Temperature is 800 DEG C, and the sintered heat insulating time is 12h, uses temperature to be washed for 60 DEG C of hot water after cooling；Drying temperature is controlled again
Degree is 60 DEG C, and boric acid nickel material is prepared in drying and processing 20h.
Embodiment 9
In molar ratio it is 3:2.2 wet ball grinding mixing 20h to uniform by nickel nitrate and boron nitride, is carried out under Oxygen Condition
It is sintered, control heating rate is 10 DEG C/min in sintering process, and sintering temperature is 900 DEG C, and the sintered heat insulating time is 3h, after cooling
It is washed using 100 DEG C of hot water；Controlling drying temperature again is 150 DEG C, and boric acid nickel material is prepared in drying and processing 4h.
Above said content is only the basic explanation under present inventive concept, and what technical solution according to the present invention was done appoints
What equivalent transformation, is within the scope of protection of the invention.
Claims (3)
1. a kind of preparation method of the negative electrode material for sodium-ion battery, it is characterised in that: nickel source and boron source are weighed, it is described
The group of any one or two kinds or more of nickel source in nickel oxide, nickel oxalate, nickel nitrate, nickel chloride or nickel sulfate
Close, any one or two kind of the boron source in diboron trioxide, boric acid, boron nitride, ammonium borate or phenyl boric acid and
The molar ratio of above combination, the nickel source and boron source is 3:2~3；After mixing, it is carried out under the conditions of oxidizing atmosphere
It is 1~20 DEG C/min that sintering, the nickel source and boron source control heating rate during the sintering process；Sintering temperature be 500~
1000℃；The sintered heat insulating time is 2-24h；Then it through supercooling, washs, the cathode material for sodium-ion battery is made in drying
Expect boric acid nickel material, chemical formula Ni3B2O6, crystal structure is orthorhombic structure, belongs to Pnnm space group.
2. the preparation method of the negative electrode material according to claim 1 for sodium-ion battery, it is characterised in that: described
Nickel source and boron source select solution mixing, stirring, wet ball grinding or dry ball milling hybrid mode one or more kinds of mixing 2~
20h。
3. the preparation method of the negative electrode material according to claim 1 for sodium-ion battery, it is characterised in that: described
Nickel source and boron source are sintered in air or oxygen.
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| CN107681141B (en) * | 2017-09-26 | 2020-11-27 | 福建师范大学 | Carbon-coated nickel borate nanorod negative electrode material of sodium ion battery |
| CN108023079B (en) * | 2017-11-30 | 2020-05-22 | 华南理工大学 | Mixed transition metal borate anode material and preparation method thereof |
| CN108539178B (en) * | 2018-04-25 | 2020-11-13 | 广东工业大学 | Novel phosphorus-sulfur-selenium composite negative electrode material for ion battery and preparation method thereof |
| CN109065879B (en) * | 2018-07-31 | 2020-10-23 | 上海电力学院 | Sodium-ion battery negative electrode material and preparation method thereof |
| CN111244444A (en) * | 2020-01-15 | 2020-06-05 | 上海电力大学 | Borate lithium ion battery cathode material and preparation method thereof |
| CN111211324A (en) * | 2020-01-15 | 2020-05-29 | 上海电力大学 | Borate lithium/sodium ion battery negative electrode material and preparation method thereof |
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