CN109065879A - A kind of anode material of lithium-ion battery and preparation method thereof - Google Patents
A kind of anode material of lithium-ion battery and preparation method thereof Download PDFInfo
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- CN109065879A CN109065879A CN201810858122.2A CN201810858122A CN109065879A CN 109065879 A CN109065879 A CN 109065879A CN 201810858122 A CN201810858122 A CN 201810858122A CN 109065879 A CN109065879 A CN 109065879A
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- lithium
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 239000010405 anode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 45
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 5
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 39
- 239000004327 boric acid Substances 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 238000009837 dry grinding Methods 0.000 claims description 4
- 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
- 238000001238 wet grinding Methods 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 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
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 3
- 238000004781 supercooling Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000001228 spectrum 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
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000003860 storage Methods 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
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910005099 Ni3Sn2 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- -1 boronic acid compound salt Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 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
- 239000007770 graphite material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 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
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 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
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002441 reversible effect Effects 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
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000035922 thirst Effects 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
- H01M4/48—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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of anode material of lithium-ion battery and preparation method thereof, molecular composition Co2Ni(BO3)2, crystal structure is rhombic system, belongs to Pnmn space group, specific steps are as follows: by nickel source, cobalt source and boron source after mixing, are sintered under the conditions of oxidizing atmosphere, and after cooling, pure phase Co is made2Ni(BO3)2Material.Compared with prior art, Co of the invention2Ni(BO3)2Material, raw material sources are extensive, it is low in cost, have a safety feature and environmental-friendly；The features such as preparation method has process flow simple, and equipment requirement is low, and product purity is high, the Co being prepared2Ni(BO3)2Material has excellent chemical property.
Description
Technical field
The present invention relates to a kind of electricity energy storage materials, more particularly, to a kind of anode material of lithium-ion battery and its preparation side
Method.
Background technique
The features such as resourceful, low in cost due to sodium, so that sodium-ion battery is increasingly becoming emerging energy-storage travelling wave tube, and
It is considered as one of the ideal alternative materials of lithium ion battery.Since sodium ion radius is much larger than lithium ion radius, so that traditional
Lithium ion battery negative material storage sodium performance it is poor, therefore, it is excellent to develop a kind of height ratio capacity, long circulation life and high rate performance
Different negative electrode material has received widespread attention.
In the cathode storage sodium material being currently known, graphite material is larger due to sodium ion radius, it is difficult in graphite linings
Deintercalation reaction is carried out, hollow Nano carbon material is also reported applied to anode material of lithium-ion battery, the results showed that have preferable
Chemical property, circulation more than 400 times after, specific capacity is still up to 251mAh/g (Nano Lett, 2012 (7), 3783-3787).
Metal and alloy type negative material are concerned by people because it is with high specific capacity, such as J.Liu passes through solvent-thermal method
It has synthesized by Ni3Sn2The Ni that nano particle assembles3Sn2Micron cage, material 1C, which is recycled 300 times, can still keep close
The reversible specific capacity (Nano Lett, 2014,14 (11), 6387-6392) of 200mAh/g.But such material is in charge and discharge cycles
Cubical expansivity is big in the process, and cycle life is undesirable.
When polyanionic boronic acid compound salt is as anode material of lithium-ion battery, there is theoretical specific capacity height, reserves
Abundant, the advantages that environmental-friendly and resource distribution is wide.Yang etc. has prepared N doping Zn using hydro-thermal method3B2O6, as sodium from
Specific capacity is up to 283.7mAh/g after sub- battery cathode recycles 100 times, and shows excellent high rate performance (Bulletin of
The Chemical Society of Japan, 2018.).The VBO that Kuang etc. is prepared using sol-gal process3Initial discharge
Specific capacity is 322.9mAh/g, but charge specific capacity be only 32.2mAh/g (Journal of Alloys&Compounds,
2017,732.).As exploration of the people to sodium-ion battery energy storage deepens continuously, people, which thirst for exploitation, has height ratio capacity, excellent
The excellent electrochemical performances such as different high rate performance and the simple new material of preparation method, to meet sodium-ion battery energy storage development
Demand.
Summary of the invention
It is negative that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of sodium-ion batteries
Pole material and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of anode material of lithium-ion battery, the molecular composition of the material are Co2Ni(BO3)2。
Preferably, the crystal structure of the material is rhombic system, is kotoite type, Pnmn space group.
A kind of preparation method of anode material of lithium-ion battery, comprising the following steps:
By nickel source, cobalt source and boron source after mixing, are sintered under the conditions of oxidizing atmosphere, after supercooling, system
Obtain pure phase Co2Ni(BO3)2Material.
Preferably, the nickel source is any one in nickel oxide, nickel oxalate, nickel nitrate, nickel chloride or nickel sulfate
Or two kinds or more of combination.
Preferably, the cobalt source is any one in cobaltosic oxide, cobalt oxalate, cobalt nitrate, cobaltous sulfate or cobalt oxide
Kind or two kinds or more of combination.
Preferably, the boron source is any one in diboron trioxide, boric acid, boron nitride, ammonium borate or phenyl boric acid
Kind or two kinds or more of combination.
Preferably, the molar ratio of the nickel source, cobalt source and boron source is 1:2:(2~3), the too low nickel easily generated of boron source, cobalt
Oxide impurity while boron excessively wastes raw material, also results in excessive boron and is difficult to remove completely in the product.
More preferred, the molar ratio of nickel source, cobalt source and boron source is 1:2:(2~2.5).
Preferably, nickel source, cobalt source and boron source mix 1~20h through dry grinding or wet grinding.
More preferred, nickel source, cobalt source and boron source mix 2~4h using dry grinding or wet grinding.
Preferably, the nickel source, cobalt source and boron source are sintered in air or oxygen.
Preferably, the process conditions of sintering are as follows: heating rate is 1~20 DEG C/min, and sintering temperature is 600~1200 DEG C,
If temperature is too low, pure phase Co cannot be made2Ni(BO3)2Material, if temperature is excessively high, the Co of possible preparation2Ni(BO3)2Material
Particle increases, and is unfavorable for ion transmission and infiltrates with electrolyte, reduces its chemical property, and the sintered heat insulating time is 1~60h.
More preferred, it is 1~15 DEG C/min that heating rate is controlled in sintering process；Sintering temperature is 700~1100 DEG C,
The sintered heat insulating time is 20~60h.
Compared with prior art, the present invention makes three kinds of members by using raw materials such as nickel source, cobalt source and boron sources, after decomposition again
Element recombinates at high temperature, obtains Co2Ni(BO3)2Material, preparation process flow is simple, low to the performance requirement of equipment, product
The features such as with high purity.Co obtained2Ni(BO3)2Material has high specific capacity and high rate performance, is a kind of with application potential
Anode material of lithium-ion battery.
Detailed description of the invention
Fig. 1 is the Co that embodiment 1 is prepared2Ni(BO3)2The XRD spectrum of material；
Fig. 2 is the Co that embodiment 1 is prepared2Ni(BO3)21st time, the 2nd time and the 3rd time charging and discharging curve figure of material；
Fig. 3 is the Co that embodiment 1 is prepared2Ni(BO3)2Cycle performance figure of the material under 200mA/g current density；
Fig. 4 is the Co that embodiment 1 is prepared2Ni(BO3)2High rate performance figure of the material under different electric current densities.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The nickel nitrate of 2.9g, the cobalt nitrate of 5.8g and 1.24g boric acid is uniform by ground and mixed, in air atmosphere condition
Under be warming up to after 900 DEG C and constant temperature keeps 55h in tube furnace with 1 DEG C/min rate, cooled to room temperature obtains product
Co2Ni(BO3)2Material.
Electrochemical property test:
By the Co of synthesis2Ni(BO3)2Negative electrode material, conductive carbon black and binder carboxymethyl cellulose (CMC) are in mass ratio
80:10:10 is uniformly mixed, and is coated on copper foil, strikes out electrode slice after dry, for 24 hours in 80 DEG C of dryings.It is to electricity with metallic sodium
Pole；With NaClO4It is dissolved in obtained in ethylene carbonate (EC)/dimethyl carbonate (DMC) mixed solution that mass ratio is 1:1
The NaClO of 1mol/L4Salting liquid is as electrolyte；Button cell is assembled into argon gas glove box.Using the blue electricity in Wuhan
CT2001A type cell tester carries out electrochemical property test, and charging/discharging voltage range is 0.01V~3.0V (compared to Na+/
Na).Test temperature is 25 DEG C.
Fig. 1 is Co2Ni(BO3)2The XRD spectrum of material, it is known from literature that the peak position of the XRD spectrum of material well with
Peak position on standard card (ICDD 75-1808) matches, and illustrates that the ingredient of material obtained is the Co of pure phase2Ni
(BO3)2.Fig. 2 is Co2Ni(BO3)21st time, the 2nd time and the 3rd time charging and discharging curve figure of material, as shown, 0.01~3.0V
Charging/discharging voltage within the scope of, in first time discharge process, there is an apparent discharge platform, and in second of discharge process
There is not identical platform, illustrates that material structure evolution occurs during first charge-discharge.In charging process three times, three
Charging curve shape is similar, apparent charging voltage platform does not occur.Fig. 3 is Co2Ni(BO3)2Material is in 200mA/g charge and discharge
Cycle performance figure under electric current density, as shown, the 2nd discharge capacity is 391.5mA/g, Co after 30 circulations2Ni
(BO3)2Capacity still keep 318.2mA/g, illustrate that inventing the material has certain chemical property.Fig. 4 is Co2Ni(BO3)2Material
Expect high rate performance figure, within the scope of the charging/discharging voltage of 0.01-3.0V, when discharge current be increased to 200mA/g, 500mA/g,
When 1000mA/g, 2000mA/g, Co2Ni(BO3)2The capacity of electrode remain respectively 382.2mAh/g, 309.7mAh/g,
245.1mAh/g,211.5mAh/g.Illustrate that inventing the material has excellent high rate performance.
Embodiment 2
The nickel nitrate of 1.5g, the cobalt nitrate of 3g and 0.7g boric acid is uniform by ground and mixed, under the conditions of air atmosphere
After being warming up to 1000 DEG C and constant temperature holding 48h in tube furnace with 5 DEG C/min rate, cooled to room temperature obtains product
Co2Ni(BO3)2Material.
Embodiment 3
By the cobalt nitrate of 6g, the nickel nitrate of 3g and 1.4g boric acid by ground and mixed it is uniform, under the conditions of air atmosphere
After being warming up to 900 DEG C and constant temperature holding 48h in tube furnace with 3 DEG C/min rate, cooled to room temperature obtains product Co2Ni
(BO3)2Material.
Embodiment 4
By the cobalt nitrate of 3g, 1.5g nickel nitrate with 0.7g boric acid by ground and mixed it is uniform, under the conditions of air atmosphere
After being warming up to 1100 DEG C and constant temperature holding 48h in tube furnace with 3 DEG C/min rate, cooled to room temperature obtains product
Co2Ni(BO3)2Material.
Embodiment 5
The cobalt nitrate of 3g, the nickel nitrate of 1.5g and 0.7g boric acid is uniform by ground and mixed, under the conditions of air atmosphere
After being warming up to 1200 DEG C and constant temperature holding 55h in tube furnace with 5 DEG C/min rate, cooled to room temperature obtains product
Co2Ni(BO3)2Material.
Embodiment 6
The cobalt nitrate of 5.8g, the nickel nitrate of 2.9g and 1.24g boric acid is uniform by ground and mixed, in air atmosphere condition
Under be warming up to after 1200 DEG C and constant temperature keeps 48h in tube furnace with 3 DEG C/min rate, cooled to room temperature obtains product
Co2Ni(BO3)2Material.
Embodiment 7
The nickel oxide of the cobaltosic oxide of 4.8g, 0.75g are mixed with 2.09g diboron trioxide by dry grinding
It is even, it is naturally cold after being warming up to 1200 DEG C and constant temperature holding 60h in tube furnace under the conditions of oxygen atmosphere with 20 DEG C/min rate
But product Co is obtained to room temperature2Ni(BO3)2Material.
Embodiment 8
The nickel oxalate of the cobalt oxalate of 2.94g, 1.47g are uniformly mixed with 0.74g boron nitride by wet grinding, in oxygen
After being warming up to 600 DEG C and constant temperature holding 20h in tube furnace under atmospheric condition with 3 DEG C/min rate, cooled to room temperature is obtained
To product Co2Ni(BO3)2Material.
Embodiment 9
The cobaltous sulfate of 5.6g, the nickel chloride of 1.3g and 5.7g ammonium borate is uniform by ground and mixed, in oxygen atmosphere item
After being warming up to 700 DEG C and constant temperature holding 1h in tube furnace under part with 10 DEG C/min rate, cooled to room temperature obtains product
Co2Ni(BO3)2Material.
Embodiment 10
The cobalt oxide of 1.5g, the nickel sulfate of 2.63g and 3.05g phenyl boric acid is uniform by ground and mixed, in air atmosphere
Under the conditions of be warming up to after 1100 DEG C and constant temperature keeps 20h in tube furnace with 15 DEG C/min rate, cooled to room temperature obtains
Product Co2Ni(BO3)2Material.
Embodiment 11
The cobalt oxalate of 2.94g, the nickel sulfate of 2.63g and 1.53g diboron trioxide is uniform by ground and mixed, in air
After being warming up to 800 DEG C and constant temperature holding 30h in tube furnace under atmospheric condition with 8 DEG C/min rate, cooled to room temperature is obtained
To product Co2Ni(BO3)2Material.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of anode material of lithium-ion battery, which is characterized in that the molecular composition of the material is Co2Ni(BO3)2。
2. a kind of anode material of lithium-ion battery according to claim 1, which is characterized in that the crystal structure of the material
For rhombic system, belong to Pnmn space group.
3. a kind of preparation method of anode material of lithium-ion battery according to claim 1, which is characterized in that including following
Step:
By nickel source, cobalt source and boron source after mixing, are sintered under the conditions of oxidizing atmosphere, after supercooling, are made pure
Phase Co2Ni(BO3)2Material.
4. a kind of preparation method of anode material of lithium-ion battery according to claim 3, which is characterized in that the nickel
Source is any one or the combination of several of them in nickel oxide, nickel oxalate, nickel nitrate, nickel chloride or nickel sulfate.
5. a kind of preparation method of anode material of lithium-ion battery according to claim 3, which is characterized in that the cobalt source
For any one or the combination of several of them in cobaltosic oxide, cobalt oxalate, cobalt nitrate, cobaltous sulfate or cobalt oxide.
6. a kind of preparation method of anode material of lithium-ion battery according to claim 3, which is characterized in that the boron
Source is any one or the combination of several of them in diboron trioxide, boric acid, boron nitride, ammonium borate or phenyl boric acid.
7. a kind of preparation method of anode material of lithium-ion battery according to claim 3, which is characterized in that the nickel
The molar ratio in source, cobalt source and boron source is 1:2:(2~3).
8. a kind of preparation method of anode material of lithium-ion battery according to claim 3, which is characterized in that mixed work
Skill condition are as follows: nickel source, cobalt source and boron source are mixed into 1~20h through dry grinding or wet grinding.
9. a kind of preparation method of anode material of lithium-ion battery according to claim 3, which is characterized in that the nickel
Source, cobalt source and boron source are sintered in air or oxygen.
10. a kind of preparation method of anode material of lithium-ion battery according to claim 3, which is characterized in that sintering
Process conditions are as follows: heating rate is 1~20 DEG C/min, and sintering temperature is 600~1200 DEG C, and the sintered heat insulating time is 1~60h.
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| 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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