CN115083792B - Nickel-vanadium-manganese oxide positive electrode material and preparation method and application thereof - Google Patents
Nickel-vanadium-manganese oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 66
- APWUUHXGDKPQHG-UHFFFAOYSA-N [O-2].[Mn+2].[V+5].[Ni+2] Chemical compound [O-2].[Mn+2].[V+5].[Ni+2] APWUUHXGDKPQHG-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 43
- 239000011733 molybdenum Substances 0.000 claims abstract description 43
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 53
- 239000011609 ammonium molybdate Substances 0.000 claims description 22
- 229940010552 ammonium molybdate Drugs 0.000 claims description 22
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 19
- 239000003990 capacitor Substances 0.000 claims description 18
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 11
- -1 ammonium molybdate hexahydrate Chemical class 0.000 claims description 11
- 229940071125 manganese acetate Drugs 0.000 claims description 11
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 11
- 229940078494 nickel acetate Drugs 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 238000009792 diffusion process Methods 0.000 abstract description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 19
- 239000010410 layer Substances 0.000 description 15
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000000227 grinding Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- CNEHAAOFZBHVPH-UHFFFAOYSA-L N.C([O-])([O-])=O.[Na+].[Na+] Chemical compound N.C([O-])([O-])=O.[Na+].[Na+] CNEHAAOFZBHVPH-UHFFFAOYSA-L 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- FUCQVSNKOWAXCC-UHFFFAOYSA-L manganese(2+);nickel(2+);diacetate Chemical compound [Mn+2].[Ni+2].CC([O-])=O.CC([O-])=O FUCQVSNKOWAXCC-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- IBRIUBQQAQEUFL-UHFFFAOYSA-N [V].[Ni].[Mn] Chemical compound [V].[Ni].[Mn] IBRIUBQQAQEUFL-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910001456 vanadium ion Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- YVGIVZYLGYEFBY-UHFFFAOYSA-L disodium carbonate hexahydrate Chemical compound O.O.O.O.O.O.C([O-])([O-])=O.[Na+].[Na+] YVGIVZYLGYEFBY-UHFFFAOYSA-L 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
Abstract
The invention provides a nickel vanadium manganese oxide positive electrode material, and a preparation method and application thereof. Molybdenum is doped in the nickel vanadium manganese oxide anode material. The preparation method comprises the following steps: and mixing a manganese source and a nickel source to obtain a mixed solution, dropwise adding a complexing agent and a precipitator into the mixed solution to react, mixing the reacted substance with the vanadium source and the molybdenum source again after the reaction is finished, and sintering to obtain the nickel-vanadium-manganese oxide anode material. According to the invention, molybdenum is doped into the nickel vanadium manganese oxide positive electrode material taking vanadium pentoxide as a main phase, so that the structural stability of the positive electrode material and the diffusion capability of lithium ions are improved, and finally the capacity and the cycle stability of the positive electrode material are improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion capacitors, and relates to a nickel-vanadium-manganese oxide positive electrode material, a preparation method and application thereof.
Background
In recent years, with the increasing market demands of new energy automobiles and large energy storage devices, the development of energy storage devices with both high power and high energy density is particularly urgent. Lithium ion batteries are currently most widely used energy storage devices, which have a high specific energy density but a low specific power density. In addition, the service life of the lithium ion battery under the condition of high-current charge and discharge can be greatly shortened. In contrast, supercapacitors have higher power densities and longer cycle lives, but lower energy densities. Lithium ion capacitors (hybrid capacitors) are a research hotspot for current energy storage systems due to the advantages of both lithium ion batteries and supercapacitors, i.e., higher energy density and power density.
The currently predominant ternary material is LiNi 1-x-y Co x Mn y O 2 However, nickel has a low discharge potential and poor conductivity; cobalt has high price and poor practicability; the excessive high manganese damages the layered structure of the material and reduces specific capacity.
CN105406055a discloses a capacitive nickel-cobalt-manganese ternary material lithium ion battery, which comprises a positive plate, a negative plate and a diaphragm, wherein the positive plate, the negative plate and the diaphragm are mutually wound or laminated at intervals, the diaphragm is arranged between the positive plate and the negative plate, the positive plate is a capacitive positive plate, the capacitive positive plate is of a three-layer composite structure, the positive plate comprises a super capacitor positive electrode layer, a lithium ion battery positive electrode layer and a positive current collector layer, the super capacitor positive electrode layer and the lithium ion battery positive electrode layer are respectively coated on the negative surface and the positive surface of the positive current collector, the super capacitor positive electrode layer is an active carbon electrode material layer, and the lithium ion battery positive electrode layer is a nickel-cobalt-manganese ternary material positive electrode material layer.
CN105406030a discloses a preparation method of a high-safety aluminum electrolytic capacitor type nickel-cobalt-manganese ternary material lithium ion battery, which comprises the steps of positive plate manufacturing, negative plate processing, winding forming and the like. In the processing of the negative plate, a negative electrode exposed area of the negative plate obtained in the negative plate manufacturing procedure is adhered with a negative aluminum foil of an aluminum electrolytic capacitor on both sides to obtain the negative plate to be wound and formed; in the winding forming process, a cylindrical battery cell is obtained by winding the positive plate, the negative plate, the diaphragm and the isolation paper in a winding mode, in the winding process, the diaphragm is arranged between the negative plate and the positive plate, the negative exposed area wraps the positive exposed area and is arranged on the circumference of the outer side of the cylindrical battery cell, and the isolation paper soaked with capacitor electrolyte is attached to the double sides of the diaphragm wound between the negative exposed area and the positive exposed area.
In the capacitor in the above document, nickel-cobalt-manganese ternary materials are used as the positive electrode materials, which has certain disadvantages.
In order to improve the defects, the ternary electrode material is prepared by nickel, vanadium and manganese metal oxides, and the main phase of the ternary electrode material is vanadium pentoxide, V 2 O 5 The lithium ion storage device has a layered structure easy to release and intercalate lithium ions, and is suitable for storing lithium ions; in addition, compared with cobalt, vanadium has the characteristics of low price, abundant reserves, high specific capacity and the like, is favored as a cathode material of a lithium ion battery, but has poor cycle stability.
Therefore, how to improve the energy density, capacity and cycle stability of the nickel-vanadium-manganese ternary material is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a nickel vanadium manganese oxide positive electrode material, and a preparation method and application thereof. According to the invention, molybdenum is doped into the nickel vanadium manganese oxide positive electrode material taking vanadium pentoxide as a main phase, so that the structural stability of the positive electrode material and the diffusion capability of lithium ions are improved, and finally the capacity and the cycle stability of the positive electrode material are improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a nickel vanadium manganese oxide cathode material doped with molybdenum.
According to the invention, molybdenum is doped into the nickel vanadium manganese oxide positive electrode material taking vanadium pentoxide as a main phase, so that the structural stability of the positive electrode material and the diffusion capability of lithium ions are improved, and finally the capacity and the cycle stability of the positive electrode material are improved.
The main phase of the positive electrode material is vanadium pentoxide, the doping of molybdenum replaces a part of vanadium, mo is a multivalent element, has similar crystal properties as V, comprises ionic radius and coordination with V, and shows oxidation-reduction potential very close to V, good metal conductivity and high chemical stability; thus, the incorporation of molybdenum expands the lattice of the material, promoting Li + Is inserted/removed; interaction of molybdenum ion with negative oxygen ion (O 2- ) Strengthen [ VO ] 5 ]Bonding of layers increases the materialIs of the structural stability of (a); the introduction of molybdenum ions improves the electron conductivity and the lithium ion diffusion capacity of the positive electrode material; in Li + In the process of embedding/extracting, local structural defects generated by introducing metal Mo ions become nucleation centers of phase change, and the cycle performance is enhanced.
Preferably, the chemical formula of the nickel vanadium manganese oxide positive electrode material without doping molybdenum is Ni 1-x-y V x Mn y O 2 0.6 < x < 1,0 < y < 1, for example, the x may be 0.65, 0.7, 0.75, 0.8, 0.85, 0.9 or 0.95, etc., and the y may be 0.05, 0.1, 0.15, 0.2, 0.3, 0.35 or 0.4, etc.
In a second aspect, the present invention provides a method for preparing the nickel vanadium manganese oxide positive electrode material according to the first aspect, the method comprising the steps of:
and mixing a manganese source and a nickel source to obtain a mixed solution, dropwise adding a complexing agent and a precipitator into the mixed solution to react, mixing the reacted substance with the vanadium source and the molybdenum source again after the reaction is finished, and sintering to obtain the nickel-vanadium-manganese oxide anode material.
According to the preparation method provided by the invention, the nickel-manganese hydroxide is prepared firstly and then mixed with the vanadium source and the molybdenum source, so that the doping of the main phase of the vanadium pentoxide can be better realized, the preparation method is simple, no complex treatment process is needed, and if the doping of the molybdenum is carried out in the nickel-manganese reaction process, the exertion of the main phase can be influenced, so that the doping of the main phase of the material cannot be realized.
Preferably, the molybdenum source is doped in an amount of 2.5 to 10wt%, for example, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.3wt%, 4.5wt%, 4.8wt%, 5wt%, 5.3wt%, 5.5wt%, 5.8wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt% or 10wt%, etc., preferably 4 to 6wt%, based on 100% by mass of the undoped nickel vanadium manganese oxide cathode material.
In the invention, the doping amount of the molybdenum source is too small to bring the advantages of Mo into play, and the doping amount is too large to exceed 10 weight percent, so that molybdenum ions occupy too much vanadium ions, and the [ VO is weakened 5 ]The bonding of the layers is performed in such a way that,thereby shortening V 2 O 5 The interlayer distance of the layered structure can not only play a role in stabilizing the structure, but also influence the normal exertion of the capacity of the undoped anode material, and when the doping amount is 4-6wt%, the capacity of the material is greatly improved, and meanwhile, the cycle stability is also obviously improved.
Preferably, the remixing process includes:
mixing the vanadium source and the molybdenum source, mixing with the reacted substance again, and drying.
In the invention, the anode material with good electrochemical performance can be obtained without special drying treatment on the re-mixed substances and sintering after common drying.
Preferably, the drying temperature is 50 to 60 ℃, for example 50 ℃, 55 ℃, 60 ℃ or the like.
Preferably, the sintering temperature is 300 to 400 ℃, for example 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃,400 ℃, or the like.
Preferably, the sintering time is 6 to 8 hours, for example 6 hours, 7 hours or 8 hours, etc.
Preferably, the nickel source comprises nickel acetate.
Preferably, the manganese source comprises manganese acetate.
Preferably, the vanadium source comprises ammonium metavanadate.
Preferably, the molybdenum source comprises ammonium molybdate hexahydrate.
Preferably, the precipitant comprises aqueous ammonia.
Preferably, the complexing agent comprises sodium carbonate.
Preferably, the dropping speed is 50-80 mL/min, for example, 50mL/min, 55mL/min, 60mL/min, 65mL/min, 70mL/min, 75mL/min or 80mL/min, etc.
Preferably, after the reaction is completed, the reacted materials are sequentially centrifuged and dried.
Preferably, the rotational speed of the centrifugation is 6000 to 8000r/min, such as 6000r/min, 6500r/min, 7000r/min, 7500r/min, 8000r/min, etc.
Preferably, the drying temperature is 80 to 100 ℃, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃,100 ℃, or the like.
Preferably, the drying time is 18 to 24 hours, for example 18 hours, 20 hours or 24 hours, etc.
As a preferred technical scheme, the preparation method comprises the following steps:
mixing a manganese source and a nickel source to obtain a mixed solution, dropwise adding a complexing agent and a precipitating agent into the mixed solution at a dropwise speed of 50-80 mL/min for reaction, centrifuging a substance obtained by the reaction at a rotating speed of 6000-8000 r/min after the reaction is finished, drying at 80-100 ℃ for 18-24 hours, adding the mixed molybdenum source and vanadium source into the dried substance, mixing again, drying at 50-60 ℃, and sintering at 300-400 ℃ for 6-8 hours to obtain the nickel-vanadium-manganese oxide anode material;
wherein the doping amount of the molybdenum source is 2.5-15 wt% based on 100% of the mass of the undoped nickel-vanadium-manganese oxide positive electrode material.
In a third aspect, the present invention also provides a lithium ion capacitor comprising the nickel vanadium manganese oxide positive electrode material according to the first aspect.
The positive electrode material provided by the invention is used in a lithium ion capacitor.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the positive electrode material provided by the invention, the nickel vanadium manganese oxide positive electrode material taking vanadium pentoxide as a main phase is doped with molybdenum, so that the electronic conductivity and lithium ion diffusion capacity of the positive electrode material are improved, the structural stability of the material is also improved, and the capacity and the cycle stability of the positive electrode material are finally improved. When the doping amount of the molybdenum source is 4-6wt% under the current density of 1000mA/g, the capacity of the battery obtained by the positive electrode material can reach more than 105mAh/g, the long-cycle stability is good, the capacity retention rate of 500 cycles is compared with the capacity retention rate of 50 cycles, the attenuation rate is below 7%, and the capacity retention rate after 500 cycles can still reach more than 80.5%; the capacity retention rate of 1000 cycles is 7.5% or less compared with that of 50 cycles, and the capacity retention rate after 1000 cycles can still reach 80.1% or more.
(2) The preparation method provided by the invention can realize the doping of the main phase of the nickel-vanadium-manganese anode material, is simple and feasible, and is suitable for actual production.
Drawings
Fig. 1 is an SEM image (including a partial magnified SEM image) of the molybdenum-doped nickel vanadium manganese oxide cathode material provided in example 1.
Fig. 2 is an SEM image (including a partial magnified SEM image) of the molybdenum-doped nickel vanadium manganese oxide positive electrode material provided in example 2.
Fig. 3 is an SEM image (including a partial magnified SEM image) of the molybdenum-doped nickel vanadium manganese oxide positive electrode material provided in example 3.
Fig. 4 is an SEM image (including a partial magnified SEM image) of the molybdenum-doped nickel vanadium manganese oxide positive electrode material provided in example 4.
Fig. 5 is an XRD pattern of the molybdenum doped nickel vanadium manganese oxide positive electrode materials provided in examples 1-4.
FIG. 6 is an XRD pattern of the molybdenum doped nickel vanadium manganese oxide positive electrode materials provided in examples 1-4 at 19.5-23.5.
Fig. 7 is a graph showing the cycle performance of the lithium ion capacitors provided in examples 1 to 4.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a molybdenum-doped nickel-vanadium-manganese oxide positive electrode material, which is prepared by the following steps:
the ternary positive electrode is prepared from ammonium metavanadate, manganese acetate, nickel acetate, ammonium molybdate hexahydrate and anhydrous sodium carbonate by weighing the ammonium metavanadate, the manganese acetate and the nickel acetate according to a molar ratio of 8:0.5:0.5
(1) Firstly, preparing manganese acetate and nickel acetate into a manganese acetate-nickel acetate mixed solution with the concentration of 0.04 mol/L; preparing 0.2mol/L sodium carbonate solution, adding ammonia water accounting for 8% of the mass of the sodium carbonate solution, uniformly mixing to obtain a sodium carbonate-ammonia water mixed solution, dropwise adding the sodium carbonate-ammonia water mixed solution into the manganese acetate-nickel acetate mixed solution at a titration speed of 50mL/min through a peristaltic pump according to the volume ratio of the mixed solution of 1:1, continuously stirring for 10min after titration is finished, standing until clear solution and precipitate are completely layered, removing the supernatant, and then performing centrifugal treatment at a rotating speed of 7000r/min for 10min for 3 times to keep precipitates; putting the precipitate obtained by centrifugation into a container, drying for 20 hours at 80 ℃, and grinding to obtain a material A;
(2) Adding 2.5wt% of ammonium molybdate (calculated by 100% of undoped nickel-vanadium-manganese, namely the material obtained by weighing the raw materials in a molar ratio in advance) into ammonium metavanadate, adding a proper amount of deionized water, stirring until the material A is completely dissolved, pouring the material A into the ammonium molybdate, heating the material A at 55 ℃ until the material A is evaporated to dryness, drying and grinding the material A again, placing the material A in a muffle furnace, sintering the material A at a high temperature for 6 hours at 400 ℃, cooling the muffle furnace to room temperature, grinding and sieving the material A to obtain Mo-doped vanadium-based ternary material Mo@V 0.76 Mn 0.032 Ni 0.029 O 2 。
Fig. 1 shows an SEM image (including a partially enlarged SEM image) of the molybdenum-doped nickel vanadium manganese oxide positive electrode material provided in example 1, in which the morphology distribution of the material is relatively uneven, and small particles are agglomerated on the surface of large particles to form irregular particles, and thus relatively irregular aggregates are formed.
Example 2
The embodiment provides a molybdenum-doped nickel-vanadium-manganese oxide positive electrode material, which is prepared by the following steps:
the ternary positive electrode is prepared from ammonium metavanadate, manganese acetate, nickel acetate, ammonium molybdate hexahydrate and anhydrous sodium carbonate by weighing the ammonium metavanadate, the manganese acetate and the nickel acetate according to a molar ratio of 8:0.5:0.5
(1) Firstly, preparing manganese acetate and nickel acetate into a manganese acetate-nickel acetate mixed solution with the concentration of 0.04 mol/L; preparing a sodium carbonate solution with the concentration of 0.2mol/L, adding ammonia water accounting for 8% of the mass of the sodium carbonate solution, uniformly mixing to obtain a sodium carbonate-ammonia water mixed solution, dripping the sodium carbonate-ammonia water mixed solution into a manganese acetate-nickel acetate mixed solution at the titration speed of 60mL/min through a peristaltic pump according to the volume ratio of the mixed solution of 1:1, continuously stirring for 10min after titration is finished, standing until clear liquid and precipitate are completely layered, removing the supernatant, and then performing centrifugal treatment at the rotating speed of 7000r/min for 10min for 3 times to keep precipitates; putting the precipitate obtained by centrifugation into a container, drying for 20 hours at 80 ℃, and grinding to obtain a material A;
(2) Then adding 5wt% of ammonium molybdate (calculated by 100% of undoped nickel-vanadium-manganese, namely the material obtained by weighing the raw materials in a molar ratio in advance) into ammonium metavanadate, adding a proper amount of deionized water, stirring until the material A is completely dissolved, pouring the material A into the ammonium molybdate, heating the material A at 55 ℃ until the material A is evaporated to dryness, drying and grinding the material A again, placing the material A in a muffle furnace, sintering the material A at a high temperature of 400 ℃ for 6 hours, cooling the muffle furnace to room temperature, grinding and sieving the material A to obtain Mo-doped vanadium-based ternary material Mo@V 0.76 Mn 0.032 Ni 0.029 O 2 。
Example 3
The embodiment provides a molybdenum-doped nickel-vanadium-manganese oxide positive electrode material, which is prepared by the following steps:
the ternary positive electrode is prepared from ammonium metavanadate, manganese acetate, nickel acetate, ammonium molybdate hexahydrate and anhydrous sodium carbonate by weighing the ammonium metavanadate, the manganese acetate and the nickel acetate according to a molar ratio of 8:0.5:0.5
(1) Firstly, preparing manganese acetate and nickel acetate into a manganese acetate-nickel acetate mixed solution with the concentration of 0.04 mol/L; preparing a sodium carbonate solution with the concentration of 0.2mol/L, adding ammonia water accounting for 8% of the mass of the sodium carbonate solution, uniformly mixing to obtain a sodium carbonate-ammonia water mixed solution, dripping the sodium carbonate-ammonia water mixed solution into the manganese acetate-nickel acetate mixed solution at the titration speed of 80mL/min through a peristaltic pump according to the volume ratio of the mixed solution of 1:1, continuously stirring for 10min after titration is finished, standing until clear liquid and precipitate are completely layered, removing the supernatant, and then performing centrifugal treatment at the rotating speed of 7000r/min for 10min for 3 times to keep precipitates; putting the precipitate obtained by centrifugation into a container, drying for 20 hours at 80 ℃, and grinding to obtain a material A;
(2) Adding 10wt% of ammonium molybdate (calculated by 100% of undoped nickel-vanadium-manganese, namely the material obtained by weighing the raw materials according to the molar ratio in advance) into ammonium metavanadate, adding a proper amount of deionized water, stirring until the material A is completely dissolved, pouring the material A into the ammonium molybdate, heating the material A at 55 ℃ until the material A is evaporated to dryness, drying and grinding the material A again, placing the material A in a muffle furnace, sintering the material A at a high temperature of 400 ℃ for 6 hours, cooling the muffle furnace to room temperature, grinding and sieving the material A to obtain Mo-doped vanadium-based ternary material Mo@V 0.76 Mn 0.032 Ni 0.029 O 2 。
Example 4
This example differs from example 1 in that ammonium molybdate is added in an amount of 15wt% in step (2) of this example.
The remaining preparation methods and parameters were consistent with example 1.
FIGS. 1-4 show SEM images (including partial magnified SEM images) of molybdenum-doped nickel vanadium manganese oxide cathode materials provided in examples 1-4, respectively, as can be seen from FIGS. 1-4, of V doped with 5wt% ammonium molybdate 0.76 Mn 0.032 Ni 0.029 O 2 The ternary material has relatively regular large-particle crystals, the surrounding particles are uniform in size and closely stacked together, the crystal form is relatively complete, and the crystal form of the material under the structure is complete, which is favorable for Li + Has better electrochemical performance.
FIG. 5 shows XRD patterns of the molybdenum-doped nickel vanadium manganese oxide cathode materials provided in examples 1-4, and FIG. 6 shows XRD patterns of the molybdenum-doped nickel vanadium manganese oxide cathode materials provided in examples 1-4 at 19.5-23.5, as can be seen from FIG. 5, comparing the doped samples with V 2 O 5 The standard card comparison of (2) shows that no impurity peak is generated, which indicates that the doping of small amount of Mo can not change the phase structure of the matrix material, and the Mo doped V is successfully synthesized 0.76 Mn 0.032 Ni 0.029 O 2 And (5) a crystal. Feeding inAs shown in FIG. 6, the XRD pattern is enlarged in one step, and as the doping amount increases, the diffraction peak starts to shift to a large angle, and as the Bragg equation shows, the smaller the angle is, the larger the plane spacing is, for Li in the interlayer structure + The more advantageous the de-embedding. Thus, comparing the results shows that XRD diffraction peaks of ternary positive electrode material doped with 5wt% ammonium molybdate are significantly shifted toward a small angle, indicating that it is more advantageous to accommodate more Li + And during the Mo doping process, partial Mo is likely to replace the original pentavalent vanadium ion, and the radius of the Mo ion is the sameVanadium ion->Large, indicating that Mo expands Li to a certain extent + A two-dimensional channel for migration, which is more beneficial to Li + Is inserted into and removed from the housing.
Fig. 7 shows a comparison of the cycling performance of the lithium ion capacitors provided in examples 1-4, and it can be seen from fig. 7 that at a current density of 1000mA/g, particularly at a doping level of 5%, the capacity is increased by 61.9% compared to the undoped (63 mAh/g) capacity, and the capacity can still reach 83mAh/g after 2000 cycles, which is much greater than the initial capacity of the undoped material. This is because the sample has superior crystal face and regular morphology, which is beneficial to promoting Li + And electron transfer, which provides faster lithium ion transfer kinetics during cycling. Meanwhile, molybdenum ions replace part of vanadium ions, and interact with negative oxygen ions (O 2- ) Can strengthen [ VO ] 5 ]The combination of the layers expands the ion migration track and also increases the structural stability of the matrix material, so that the obtained spatial structure is beneficial to improving the mechanical stability of the electrode material, thereby improving the electrochemical performance of the electrode material.
Example 5
This example differs from example 1 in that ammonium molybdate is added in an amount of 2wt% in step (2) of this example.
The remaining preparation methods and parameters were consistent with example 1.
Example 6
This example differs from example 1 in that ammonium molybdate is added in an amount of 4wt% in step (2) of this example.
The remaining preparation methods and parameters were consistent with example 1.
Example 7
This example differs from example 1 in that ammonium molybdate is added in an amount of 6wt% in step (2) of this example.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The difference between this comparative example and example 1 is that ammonium molybdate was not added in step (2) of this comparative example.
The remaining preparation methods and parameters were consistent with example 1.
The positive electrode materials Super-P and PVDF provided in examples 1 to 7 and comparative example 1 were mixed and made into paste according to a mass ratio of 8:1:1, coated on an aluminum foil on one side, dried in a vacuum drying oven at 70℃for 12 hours, and then made into an electrode.
Assembling a capacitor cell:
the capacitor cell comprises a lithium metal cathode, a diaphragm, and an electrolyte (solute: 1 mol/LLiPF) 6 Solvent: EC/EMC/DMC,1:1:1 vol.%), electrodes provided in examples 1-7 and comparative example 1, battery case. The battery assembly process is as follows:
placing a composite electrode material in a battery housing; 2. two diaphragms are taken and evenly dipped with electrolyte in a weighing bottle and sequentially placed on a pole piece; 3. a small amount of electrolyte in the volumetric flask is sucked by a disposable dropper, 2mL of electrolyte is needed, and then 0.3mL of electrolyte is dripped on the two layers of diaphragms; 4. placing a lithium sheet over the separator; 5. a gasket with the thickness of 1mm and an elastic sheet are sequentially arranged on the lithium sheet; 6. the battery case is covered.
The batteries provided in examples 1 to 7 and comparative example 1 were subjected to an electrochemical performance test at a large current of 1000mA/g, and the cycle performance and capacity results thereof are shown in Table 1.
TABLE 1
From the data of examples 2, 6 and 7, it is understood that the addition of ammonium molybdate at 4 to 6wt% not only improves the capacity of the positive electrode material, but also greatly improves the cycle stability, particularly the long cycle stability.
From the data of examples 1 to 5, it is understood that the addition amount of ammonium molybdate (molybdenum source) is too large to be more than 10wt%, not only the cycle performance of the material cannot be improved, but also the material capacity is worse due to the reverse, and the addition amount of ammonium molybdate is too small to affect the cycle stability of the material.
From the data of examples 1-4, examples 6 and 7 and comparative example 1, it is understood that the nickel vanadium manganese oxide positive electrode material provided by the present invention has improved capacity and cycle stability by doping molybdenum.
In conclusion, the positive electrode material provided by the invention promotes Li by doping molybdenum into the nickel vanadium manganese oxide positive electrode material taking vanadium pentoxide as a main phase + And the diffusion and electron transfer of the lithium ion battery lead to faster lithium ion transfer kinetics in the circulation process; meanwhile, molybdenum ions replace part of vanadium ions, and interact with negative oxygen ions (O 2- ) Can strengthen [ VO ] 5 ]The combination of the layers expands the ion migration track and also increases the structural stability of the matrix material, so that the obtained space structure is beneficial to improving the mechanical stability of the electrode material, and finally the capacity and the cycle stability of the positive electrode material are improved. When the doping amount of the molybdenum source is 4-6wt% under the current density of 1000mA/g, the capacity of the battery obtained by the positive electrode material can reach more than 105mAh/g, the long-cycle stability is good, the capacity retention rate of 500 cycles is compared with the capacity retention rate of 50 cycles, the attenuation rate is below 7%, and the capacity retention rate after 500 cycles can still reach more than 80.5%; the capacity retention rate of 1000 cycles is 7.5% or less compared with that of 50 cycles, and the capacity retention rate after 1000 cycles can still reach 80.1% or more.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (15)
1. The nickel-vanadium-manganese oxide positive electrode material is characterized in that the main phase of the nickel-vanadium-manganese oxide positive electrode material is vanadium pentoxide; molybdenum is doped in the nickel vanadium manganese oxide anode material;
the nickel vanadium manganese oxide positive electrode material is prepared by the following preparation method, which comprises the following steps:
mixing a manganese source and a nickel source to obtain a mixed solution, dropwise adding a complexing agent and a precipitator into the mixed solution to react, mixing the reacted substance with the vanadium source and the molybdenum source again after the reaction is finished, and sintering to obtain the nickel-vanadium-manganese oxide anode material; the doping amount of the molybdenum source is 4-6wt% based on 100% of the mass of the undoped nickel-vanadium-manganese oxide positive electrode material; the molybdenum source comprises ammonium molybdate hexahydrate;
the sintering temperature is 300-400 ℃;
the sintering time is 6-8 hours;
the remixing process includes:
firstly mixing a vanadium source and a molybdenum source, then mixing the mixture with the reacted substance again, and drying; the vanadium source includes ammonium metavanadate.
2. The nickel vanadium manganese oxide positive electrode material according to claim 1, wherein the chemical formula of the nickel vanadium manganese oxide positive electrode material without doped molybdenum is Ni 1-x-y V x Mn y O 2 ，0.6＜x＜1，0＜y＜1。
3. A method for preparing the nickel vanadium manganese oxide positive electrode material according to claim 1 or 2, comprising the steps of:
mixing a manganese source and a nickel source to obtain a mixed solution, dropwise adding a complexing agent and a precipitator into the mixed solution to react, mixing the reacted substance with the vanadium source and the molybdenum source again after the reaction is finished, and sintering to obtain the nickel-vanadium-manganese oxide anode material; the doping amount of the molybdenum source is 4-6wt% based on 100% of the mass of the undoped nickel-vanadium-manganese oxide positive electrode material; the molybdenum source comprises ammonium molybdate hexahydrate;
the remixing process includes:
firstly mixing a vanadium source and a molybdenum source, then mixing the mixture with the reacted substance again, and drying; the vanadium source includes ammonium metavanadate.
4. The method for producing a nickel vanadium manganese oxide positive electrode material according to claim 3, wherein the drying temperature is 50 to 60 ℃.
5. The method of preparing a nickel vanadium manganese oxide positive electrode material according to claim 3, wherein the nickel source comprises nickel acetate.
6. The method of preparing a nickel vanadium manganese oxide positive electrode material according to claim 3, wherein the manganese source comprises manganese acetate.
7. The method for preparing a nickel vanadium manganese oxide positive electrode material according to claim 3, wherein the precipitant comprises ammonia water.
8. The method for preparing a nickel vanadium manganese oxide positive electrode material according to claim 3, wherein the complexing agent comprises sodium carbonate.
9. The method for preparing a nickel-vanadium-manganese oxide positive electrode material according to claim 3, wherein the dropping speed is 50-80 mL/min.
10. The method for producing a nickel vanadium manganese oxide positive electrode material according to claim 3, wherein after the completion of the reaction, the reacted material is centrifuged and dried in this order.
11. The method for preparing a nickel vanadium manganese oxide positive electrode material according to claim 10, wherein the rotational speed of the centrifugation is 6000-8000 r/min.
12. The method for preparing a nickel vanadium manganese oxide positive electrode material according to claim 10, wherein the drying temperature is 80 to 100 ℃.
13. The method for preparing a nickel vanadium manganese oxide positive electrode material according to claim 10, wherein the drying time is 18 to 24 hours.
14. The method for preparing a nickel vanadium manganese oxide positive electrode material according to claim 3, comprising the steps of:
mixing a manganese source and a nickel source to obtain a mixed solution, dropwise adding a complexing agent and a precipitating agent into the mixed solution at a dropwise speed of 50-80 mL/min for reaction, centrifuging a substance obtained by the reaction at a rotating speed of 6000-8000 r/min after the reaction is finished, drying at 80-100 ℃ for 18-24 hours, adding the mixed molybdenum source and vanadium source into the dried substance, mixing again, drying at 50-60 ℃, and sintering at 300-400 ℃ for 6-8 hours to obtain the nickel-vanadium-manganese oxide anode material;
wherein the doping amount of the molybdenum source is 4-6wt% based on 100% of the mass of the undoped nickel-vanadium-manganese oxide positive electrode material.
15. A lithium ion capacitor, characterized in that the capacitor comprises the nickel vanadium manganese oxide positive electrode material according to claim 1 or 2.
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