CN103413938A - Pyrovandate cathode material of lithium-ion battery and preparation method of pyrovandate cathode material - Google Patents

Pyrovandate cathode material of lithium-ion battery and preparation method of pyrovandate cathode material Download PDF

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CN103413938A
CN103413938A CN2013101185142A CN201310118514A CN103413938A CN 103413938 A CN103413938 A CN 103413938A CN 2013101185142 A CN2013101185142 A CN 2013101185142A CN 201310118514 A CN201310118514 A CN 201310118514A CN 103413938 A CN103413938 A CN 103413938A
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ion battery
lithium ion
pyrovanadate
negative material
pyrovandate
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倪世兵
吕小虎
杨学林
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China Three Gorges University CTGU
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China Three Gorges University CTGU
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a pyrovandate cathode material of a lithium-ion battery and a preparation method of the pyrovandate cathode material. The pyrovandate cathode material is characterized by utilizing a hydrothermal method, adopting ammonium metavanadate or vanadium pentoxide and zinc nitrate, anhydrous copper sulfate or cobalt nitrate as main reagents, hexamethylenetetramine as a reaction promoter and sodium sulfate as the soluble ion salt to synthesize the cathode material pyrovandate M3(OH)2V2O7, wherein M is Zn, Co and Cu. The pyrovandate cathode material prepared according to the method is simple in synthesis process, easy to operate and low in preparation cost; the obtained sample is good in crystallization performance and good in crystalline form; the method has universality and can be used for synthesizing the pyrovandate series; the prepared material has the characteristic of high discharging capacity.

Description

A kind of lithium ion battery pyrovanadate negative material and preparation method
Technical field
The present invention relates to a class Novel cathode material for lithium ion battery, particularly a kind of vanadium pyro acid salt M 3(OH) 2V 2O 7The technology of preparing of (M=Zn, Co, Cu) and storage lithium characteristic thereof, belong to field of electrochemical power source.
Background technology
Lithium ion battery is the third generation small battery after nickel-cadmium cell, Ni-MH battery, have the advantages such as operating voltage is high, specific energy large, the discharge potential curve is steady, self discharge is little, have extended cycle life, cryogenic property is good, memoryless, pollution-free, can meet portable type electronic product miniaturization, lightweight, free of contamination requirement.Lithium ion battery has been widely used in the electronic products such as mobile communication, notebook computer at present, but, as the power supply as mobile devices such as electric vehicle, artificial satellite, field operations communications, also needs further to improve specific energy and the power of battery.The key of research and development high-energy-density, high power lithium ion cell is to design and prepare the electrode material of high power capacity, high rate capability.At present, positive electrode is generally to contain lithium transition group metallic oxide (LiCoO 2, LiFePO 4, LiN 1-y-zMn yCo zO zDeng), the possibility that increases substantially the positive electrode specific capacity on existing positive electrode architecture basics is little, further improves the significantly raising that capacity of lithium ion battery can only rely on the negative material capacity.Traditional graphite cathode material theoretical capacity is lower, and the research and development Novel cathode material for lithium ion battery becomes a key factor that affects the lithium ion battery development.Vanadium pyro acid salt M 3(OH) 2V 2O 7(M=Zn, Co, Cu) has special stratiform, channel design, can be used as lithium ion and embeds/take off the embedding carrier.We show early-stage Study, Zn 3(OH) 2V 2O 7Nanometer sheet has shown obvious discharge platform and 618mAhg as lithium ion battery negative material -1Discharge capacity, far above the graphitic carbon material, potential application is arranged in lithium ion battery.At present, about M 3(OH) 2V 2O 7Preparation and Electrochemical Properties carry out lessly, for M 3(OH) 2V 2O 7System lacks preparation method's research of system.Zn prepared by existing a small amount of liquid phase and solid phase synthesis process 3(OH) 2V 2O 7And Cu 3(OH) 2V 2O 7Crystal property is bad, and its performance is had to obvious impact.Therefore, a kind of vanadium pyro acid salt M with well-crystallized performance of invention 3(OH) 2V 2O 7The preparation method of (M=Zn, Co, Cu) series also studies its chemical property as lithium ion battery negative material and has great importance.Research shows, soluble ionic salt such as Na 2SO 4, K 2SO 4, NaCl, KCl etc. have special effect in solution, can affect nucleation and crystal growing process in solution, promote crystallization and the pattern optimization of material.Based on above background, the application promotes vanadium pyro acid salt M by Hydrothermal Synthesis, introducing soluble ionic salt 3(OH) 2V 2O 7The crystalline growth of (M=Zn, Co, Cu), prepare nanometer-submicron level, has the vanadium pyro acid salt of special appearance and its chemical property as lithium ion battery negative material is assessed.
Summary of the invention
Purpose of the present invention is exactly the impact by means of crystal growth in soluble ion salt pair solution environmental, prepares the Novel cathode material for lithium ion battery vanadium pyro acid salt M that crystal property is good 3(OH) 2V 2O 7(M=Zn, Co, Cu).Its principle utilizes hydro-thermal reaction to provide energy for reaction raw materials exactly, reaction raw materials is first dissolved and chemical reaction occurs gradually, simultaneously, utilize cation and the anion of in soluble ionic salt, not participating in reaction directly to regulate the chemical reaction between reaction raw materials, control chemical reaction velocity, finally obtain the vanadium pyro acid salt series that crystal property is good.
Vanadium pyro acid salt M involved in the present invention 3(OH) 2V 2O 7(M=Zn, Co, Cu) serial synthesis material is ammonium metavanadate, zinc nitrate, cobalt nitrate, cupric sulfate pentahydrate, hexamethylenetetramine, sodium sulphate, potassium sulfate etc.The reaction occurred in hydrothermal reaction process is:
(CH 2 ) 6N 4 +10H 2O → 6HCHO + 4NH 3·H 2O (1)
NH 3·H 2O → OH - + [NH 4] + (2)
NH 4VO 3→ VO 3 - + [NH 4] +
2VO 3 - + (n+3)OH - + 3M 2+ + (n-1)H + → 2M 3(OH) 2 V 2O 7·nH 2O (3)
In the present invention, soluble ionic salt is not participated in reaction directly, but composition, structure and the pattern of product is played to crucial impact.The present invention prepares vanadium pyro acid salt M 3(OH) 2V 2O 7(M=Zn, Co, Cu) serial needed raw material is ammonium metavanadate and zinc nitrate, cobalt nitrate, cupric sulfate pentahydrate, six methine four ammonia, sodium sulphate.When in reaction raw materials, not obtaining vanadium pyro acid salt when six methine four ammonia.When the vanadium pyro acid salt that can not obtain having the well-crystallized performance during without soluble ionic salt in reaction raw materials.In the material preparation process, first ammonium metavanadate and zinc nitrate or cobalt acetate or cupric sulfate pentahydrate and six methine four ammonia and the reaction raw materials such as sodium sulphate or potassium sulfate adding distil water in beaker were stirred 30 minutes, then uniform solution is transferred in polytetrafluoroethylene hydro-thermal axe inner bag, in baking oven, be heated to 90 ~ 200 degree reaction 12 ~ 24 hours, naturally cooling and eccentric cleaning can obtain vanadium pyro acid salt sample.The gained material toasts 24 hours for the preparation of electrode with infrared lamp in air.
The preparation method of vanadium pyro acid salt negative material involved in the present invention has following outstanding feature:
(1) synthesis technique is simple, easy operating, and the material preparation cost is low;
(2) gained sample crystal property is good, good crystalline;
(3) method has universality, can be used for vanadium pyro acid salt series synthetic;
(4) prepared material discharging capacity is higher.
The accompanying drawing explanation
Fig. 1 (a), (b), (c) are respectively the Zn prepared through embodiment 3,6,9 3(OH) 2V 2O 7NH 2O, Cu 3(OH) 2V 2O 7NH 2O, Co 3(OH) 2V 2O 7NH 2The XRD collection of illustrative plates of O.
Fig. 2 (a), (b), (c) are respectively the Zn prepared through embodiment 3,6,9 3(OH) 2V 2O 7NH 2O, Cu 3(OH) 2V 2O 7NH 2O, Co 3(OH) 2V 2O 7NH 2The SEM collection of illustrative plates of O.
Fig. 3 (a), (b), (c) are respectively the Zn prepared through embodiment 3,6,9 3(OH) 2V 2O 7NH 2O, Cu 3(OH) 2V 2O 7NH 2O, Co 3(OH) 2V 2O 7NH 2The discharge curve first of O.
Embodiment
Embodiment 1. weighing V 2O 5, zinc nitrate and six appropriate methine four ammonia (V 2O 5With the ratio of zinc nitrate according to 1:3), and add appropriate distilled water and in beaker, stirred 30 minutes, the gained suspension-turbid liquid is moved in polytetrafluoroethylliner liner hydro-thermal reaction axe, reaction is 12 hours under 90 ℃ of conditions, and result shows, and prepared sample is Zn 3(OH) 2V 2O 7NH 2O.Prepared Zn 3(OH) 2V 2O 7NH 2O is banded pattern, and mean breadth is 150 nm approximately, and length is 1 ~ 3 mm.As lithium ion battery negative material, show that discharge capacity is 520 mAhg first -1.
Embodiment 2. weighing V 2O 5, zinc nitrate, six appropriate methine four ammonia and sodium sulphate (V 2O 5With the ratio of zinc nitrate according to 1:3), then add appropriate distilled water and in beaker, stirred 30 minutes, the gained suspension-turbid liquid is moved in polytetrafluoroethylliner liner hydro-thermal reaction axe, reaction is 18 hours under 120 ℃ of conditions.Prepare Zn 3(OH) 2V 2O 7NH 2O.Prepared Zn 3(OH) 2V 2O 7NH 2O is sheet, and average thickness is 100 nm approximately, and size is 1 ~ 5 mm approximately.As lithium ion battery negative material, show that discharge capacity is 560 mAhg first -1.
Embodiment 3. weighing ammonium metavanadates, zinc nitrate, appropriate six methine four ammonia and sodium sulphate (ammonium metavanadate and zinc nitrate are according to the ratio of 2:3), then adding appropriate distilled water stirred 30 minutes in beaker, the gained homogeneous solution is moved in polytetrafluoroethylliner liner hydro-thermal reaction axe, and reaction is 24 hours under 200 ℃ of conditions.Prepare the Zn of crystal property excellence 3(OH) 2V 2O 7NH 2O.The XRD collection of illustrative plates of resulting sample in Fig. 1 (a) embodiment 3, all diffraction maximum and the pyrovanadic acid zinc (Zn of hexagonal crystal system in figure 3(OH) 2V 2O 7NH 2O) correspondence, lattice constant are a=0.6049 nm, and c=0.7196 nm, corresponding to XRD card JCPDS, No. 50-0570.Strong and sharp-pointed diffraction maximum shows, prepared pyrovanadic acid zinc crystal property is good.Prepared Zn 3(OH) 2V 2O 7NH 2O is the pattern rule, the sheet of size uniform, and average thickness is 50 nm approximately, and diameter is 2 ~ 4 mm.As lithium ion battery negative material, show that discharge capacity is 618 mAhg first -1.
Embodiment 4. weighing V 2O 5, cupric sulfate pentahydrate and six appropriate methine four ammonia (V 2O 5With the ratio of cupric sulfate pentahydrate according to 1:3), and add appropriate distilled water and in beaker, stirred 30 minutes, then the gained suspension-turbid liquid is moved in polytetrafluoroethylliner liner hydro-thermal reaction axe, reaction is 12 hours under 90 ℃ of conditions, result shows, prepared sample is the mixture of barium oxide and copper hydroxide.
Embodiment 5. weighing V 2O 5, cupric sulfate pentahydrate, six appropriate methine four ammonia and sodium sulphate (V 2O 5With the ratio of cupric sulfate pentahydrate according to 1:3), then add appropriate distilled water and in beaker, stirred 30 minutes, the gained suspension-turbid liquid is moved in polytetrafluoroethylliner liner hydro-thermal reaction axe, reaction is 18 hours under 120 ℃ of conditions.Result shows, prepared sample is Cu 3(OH) 2V 2O 7NH 2The O particle, the about 200nm of granularity average-size.Prepared Cu 3(OH) 2V 2O 7NH 2The O particle shows that as lithium ion battery electrode material discharge capacity is 720 mAhg first -1.
Embodiment 6. weighing ammonium metavanadates, cupric sulfate pentahydrate, appropriate six methine four ammonia and sodium sulphate (ammonium metavanadate and cupric sulfate pentahydrate are according to the ratio of 2:3), then adding appropriate distilled water stirred 30 minutes in beaker, the gained homogeneous solution is moved in polytetrafluoroethylliner liner hydro-thermal reaction axe, and reaction is 24 hours under 200 ℃ of conditions.The Cu prepared 3(OH) 2V 2O 7NH 2O crystal property excellence, Fig. 1 (b) is the XRD collection of illustrative plates of resulting sample in embodiment 6, all diffraction maximum and monoclinic pyrovanadic acid copper (Cu in figure 3(OH) 2V 2O 7NH 2O) correspondence, lattice constant is a=1.061 nm, b=0.586nm, c=0.7260 nm, corresponding to XRD card JCPDS, the diffraction maximum that No. 46-1443. is strong and sharp-pointed shows, prepared pyrovanadic acid copper crystal property is good.The Cu of even size distribution 3(OH) 2V 2O 7NH 2The O nano particle, granularity is less than 100nm.With prepared Cu 3(OH) 2V 2O 7NH 2The O nano particle shows that as lithium ion battery electrode material discharge capacity is 875 mAhg first -1.
Embodiment 7. weighing V 2O 5, cobalt nitrate and six appropriate methine four ammonia (V 2O 5With the ratio of cobalt nitrate according to 1:3), and add appropriate distilled water and in beaker, stirred 30 minutes, the gained suspension-turbid liquid is moved in polytetrafluoroethylliner liner hydro-thermal reaction axe, reaction is 12 hours under 90 ℃ of conditions, result shows, prepared sample is the mixture of barium oxide and cobalt/cobalt oxide.
Embodiment 8. weighing V 2O 5, cobalt nitrate, six appropriate methine four ammonia and sodium sulphate (V 2O 5With the ratio of five cobalt nitrates according to 1:3), then add appropriate distilled water and in beaker, stirred 30 minutes, the gained suspension-turbid liquid is moved in polytetrafluoroethylliner liner hydro-thermal reaction axe, reaction is 18 hours under 120 ℃ of conditions.Result shows, prepared sample XRD diffraction result and Zn 3(OH) 2V 2O 7NH 2O is similar, the analysis showed that it is due to Co 2+Replaced Zn 2+, obtained Co 3(OH) 2V 2O 7NH 2O.Prepared Co 3(OH) 2V 2O 7NH 2O is irregular of pattern and particle, the about 100nm of sheet thickness, and the about 2mm of size, particle size is 200 nm ~ 1mm.With prepared Co 3(OH) 2V 2O 7NH 2O shows that as lithium ion battery negative material discharge capacity is 682 mAhg first -1.
Embodiment 9. weighing ammonium metavanadates, cobalt nitrate, appropriate six methine four ammonia and sodium sulphate (ammonium metavanadate and cobalt nitrate are according to the ratio of 2:3), then adding appropriate distilled water stirred 30 minutes in beaker, the gained homogeneous solution is moved in polytetrafluoroethylliner liner hydro-thermal reaction axe, and reaction is 24 hours under 200 ℃ of conditions.Prepare the Co of crystal property excellence 3(OH) 2V 2O 7NH 2O, Fig. 1 (c) are the XRD collection of illustrative plates of resulting sample in embodiment 9, and the diffraction maximum in figure is can't be directly corresponding with the XRD standard card of the existing compound that contains cobalt, vanadium, oxygen element, but with the pyrovanadic acid zinc (Zn of hexagonal crystal system 3(OH) 2V 2O 7NH 2O) meet finely.Due to Co 2+With Zn 2+Have similar ionic radius and electronic structure, we think, under similar synthesis condition, and Co 2+Replaced the Zn in pyrovanadic acid zinc 2+Thereby, prepared pyrovanadic acid cobalt (Co 3(OH) 2V 2O 7NH 2O), strong and sharp-pointed diffraction maximum shows, prepared pyrovanadic acid cobalt crystal property is good.Be the regular sheet with special hexagonal configuration, the about 100nm of thickness, the about 5mm of size, with prepared Co 3(OH) 2V 2O 7NH 2The O micron film shows that as lithium ion battery negative material discharge capacity is 730 mAhg first -1.

Claims (10)

1. lithium ion battery pyrovanadate negative material, it is characterized in that utilizing hydro thermal method, with ammonium metavanadate or vanadic oxide, zinc nitrate or anhydrous cupric sulfate or cobalt nitrate are main reaction reagent, hexamethylenetetramine is reaction promoter, sodium sulphate is for being soluble ionic salt, synthetic negative material pyrovanadate M 3(OH) 2V 2O 7(M=Zn, Co, Cu) series.
2. lithium ion battery pyrovanadate negative material according to claim 1, is characterized in that: Zn 3(OH) 2V 2O 7For the nanometer-submicron level laminated structure, thickness is 40-60nm, and diameter is 2-4mm.
3. lithium ion battery pyrovanadate negative material according to claim 1, is characterized in that: Zn 3(OH) 2V 2O 7Discharge capacity is 520-618mAhg first -1.
4. lithium ion battery pyrovanadate negative material according to claim 1, is characterized in that: Cu 3(OH) 2V 2O 7For nanoparticle structure, granularity is for being less than 100nm.
5. lithium ion battery pyrovanadate negative material according to claim 1, is characterized in that: Cu 3(OH) 2V 2O 7Discharge capacity is 720-875mAhg first -1.
6. lithium ion battery pyrovanadate negative material according to claim 1, is characterized in that: Co 3(OH) 2V 2O 7For the nanometer-submicron level laminated structure, thickness is less than 100nm, and diameter is 3-6mm.
7. lithium ion battery pyrovanadate negative material according to claim 1, is characterized in that: Co 3(OH) 2V 2O 7Discharge capacity is 682-730mAhg first -1.
8. lithium ion battery pyrovanadate negative material according to claim 1, it is characterized in that: the mass ratio of ammonium metavanadate and zinc nitrate or anhydrous cupric sulfate or cobalt nitrate is 2:3.
9. lithium ion battery pyrovanadate negative material according to claim 1, it is characterized in that: the mass ratio of vanadic oxide and zinc nitrate or anhydrous cupric sulfate or cobalt nitrate is 1:3.
10. lithium ion battery pyrovanadate negative material according to claim 1, is characterized in that: at 90-200 ℃ of Water Under thermal response 12-24 hour.
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Cited By (12)

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Publication number Priority date Publication date Assignee Title
CN103730642A (en) * 2014-01-24 2014-04-16 厦门大学 Negative electrode material of lithium ion battery and preparation method thereof
CN103825025A (en) * 2014-02-27 2014-05-28 三峡大学 Negative electrode material FeVO4 of lithium ion battery and preparation method thereof
CN105576234A (en) * 2014-10-13 2016-05-11 三峡大学 Lithium-ion battery NiCrxOy negative electrode material and preparation method thereof
CN106784816A (en) * 2016-12-23 2017-05-31 石家庄学院 Alkali formula vanadic acid cobalt micron sheet material and preparation method thereof
CN108346795A (en) * 2018-01-25 2018-07-31 三峡大学 A kind of water system Zinc ion battery negative material Zn3(OH)2V2O7·2H2The preparation method of O
CN110479243A (en) * 2019-09-03 2019-11-22 陕西科技大学 A kind of flower-shaped Zn3(OH)2V2O7·2H2O photochemical catalyst and preparation method thereof
CN113684487A (en) * 2021-08-30 2021-11-23 哈尔滨工业大学 Preparation method of three-dimensional foam copper-loaded basic cobalt vanadate functional material electrolytic water catalyst
CN113772727A (en) * 2021-09-06 2021-12-10 长沙学院 Preparation method and application of iron-doped copper pyrovanadate material
CN114156451A (en) * 2021-11-30 2022-03-08 安徽师范大学 Carbon cloth composite material with surface growing three-dimensional structure zinc pyrovanadate nanosheets, preparation method of carbon cloth composite material and rechargeable battery
CN114335499A (en) * 2021-12-17 2022-04-12 黑龙江省能源环境研究院 Cobalt vanadium lithium ion battery cathode material with cross structure and preparation method thereof
CN115043429A (en) * 2022-06-24 2022-09-13 重庆镁储新材料科技有限公司 Preparation method of layered hydroxyl copper pyrovanadate anode material
CN115536067A (en) * 2022-11-03 2022-12-30 南昌大学 Novel self-assembled vanadium strong hydrophobic material and preparation method thereof, and coating and preparation method thereof

Non-Patent Citations (3)

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SHIBING NI ET AL.: ""Hydrothermal synthesis of Cu3(OH)2V2O7•nH2O nanoparticles and its application in lithium ion battery"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
SHIBING NI ET AL.: ""Hydrothermal synthesis of Zn3(OH)2V2O7•nH2O nanosheets and its application in lithium ion battery"", 《MATERIALS LETTERS》 *
SHIBING NI ET AL.: ""Synthesis of Co3(OH)2V2O7•1.7H2O nanosheets and its application in lithium ion batteries"", 《MATERIALS LETTERS》 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103730642A (en) * 2014-01-24 2014-04-16 厦门大学 Negative electrode material of lithium ion battery and preparation method thereof
CN103825025A (en) * 2014-02-27 2014-05-28 三峡大学 Negative electrode material FeVO4 of lithium ion battery and preparation method thereof
CN103825025B (en) * 2014-02-27 2016-01-27 三峡大学 A kind of lithium ion battery negative material FeVO4 and preparation method thereof
CN105576234A (en) * 2014-10-13 2016-05-11 三峡大学 Lithium-ion battery NiCrxOy negative electrode material and preparation method thereof
CN106784816A (en) * 2016-12-23 2017-05-31 石家庄学院 Alkali formula vanadic acid cobalt micron sheet material and preparation method thereof
CN106784816B (en) * 2016-12-23 2020-07-14 石家庄学院 Basic cobalt vanadate micron sheet material and preparation method thereof
CN108346795A (en) * 2018-01-25 2018-07-31 三峡大学 A kind of water system Zinc ion battery negative material Zn3(OH)2V2O7·2H2The preparation method of O
CN110479243A (en) * 2019-09-03 2019-11-22 陕西科技大学 A kind of flower-shaped Zn3(OH)2V2O7·2H2O photochemical catalyst and preparation method thereof
CN113684487A (en) * 2021-08-30 2021-11-23 哈尔滨工业大学 Preparation method of three-dimensional foam copper-loaded basic cobalt vanadate functional material electrolytic water catalyst
CN113772727A (en) * 2021-09-06 2021-12-10 长沙学院 Preparation method and application of iron-doped copper pyrovanadate material
CN114156451A (en) * 2021-11-30 2022-03-08 安徽师范大学 Carbon cloth composite material with surface growing three-dimensional structure zinc pyrovanadate nanosheets, preparation method of carbon cloth composite material and rechargeable battery
CN114156451B (en) * 2021-11-30 2023-11-03 安徽师范大学 Carbon cloth composite material with three-dimensional structure zinc pyrovanadate nanosheets grown on surface, preparation method of carbon cloth composite material and rechargeable battery
CN114335499A (en) * 2021-12-17 2022-04-12 黑龙江省能源环境研究院 Cobalt vanadium lithium ion battery cathode material with cross structure and preparation method thereof
CN114335499B (en) * 2021-12-17 2024-01-26 黑龙江省能源环境研究院 Cobalt vanadium lithium ion battery anode material with crisscross structure and preparation method thereof
CN115043429A (en) * 2022-06-24 2022-09-13 重庆镁储新材料科技有限公司 Preparation method of layered hydroxyl copper pyrovanadate anode material
CN115536067A (en) * 2022-11-03 2022-12-30 南昌大学 Novel self-assembled vanadium strong hydrophobic material and preparation method thereof, and coating and preparation method thereof
CN115536067B (en) * 2022-11-03 2023-10-03 南昌大学 Self-assembled vanadium-based strong hydrophobic material, preparation method thereof, coating and preparation method thereof

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Application publication date: 20131127