CN106328943A - Method for preparing lithium vanadium phosphate (positive electrode material) of lithium ion cell - Google Patents
Method for preparing lithium vanadium phosphate (positive electrode material) of lithium ion cell Download PDFInfo
- Publication number
- CN106328943A CN106328943A CN201610993929.8A CN201610993929A CN106328943A CN 106328943 A CN106328943 A CN 106328943A CN 201610993929 A CN201610993929 A CN 201610993929A CN 106328943 A CN106328943 A CN 106328943A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- lithium
- phosphate
- vanadium phosphate
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for preparing a lithium vanadium phosphate (positive electrode material) of a lithium ion cell. The method comprises the following steps: carrying out reaction on trivalent vanadium source compound and alkali, thereby acquiring vanadium hydroxide, wherein the trivalent vanadium source compound is vanadium sulphate and/or vanadium chloride; carrying out reaction on vanadium hydroxide and phosphoric acid, thereby acquiring vanadium phosphate; mixing vanadium phosphate with lithium hydroxide or lithium carbonate and sintering, thereby acquiring the lithium vanadium phosphate (positive electrode material) of the lithium ion cell. According to the method, instead of the toxic pentavalent vanadium source compound, trivalent vanadium sulphate or vanadium chloride is utilized to prepare vanadium phosphate, so that the technique is more environmentally friendly. The step of reducing the pentavalent vanadium source compound is avoided in the vanadium phosphate preparation process, so that the technological process is shortened, the operation is simple and the industrial production is easily realized.
Description
Technical field
The invention belongs to field of lithium ion battery material, specifically, relate to one and prepare anode material for lithium-ion batteries
The method of phosphoric acid vanadium lithium.
Background technology
Common, socioeconomic development speed is the fastest, and the needs of the energy are the most increasing, meanwhile, along with fossil energy
The ecological deterioration problem that the most exhausted and combusts fossil energy in source brings becomes increasingly conspicuous.In order to reduce the utilization of fossil energy,
People increasingly pay close attention to the development of electric automobile.In the electrokinetic cell that existing electric automobile uses, lithium ion battery is because of tool
Have that energy density is high, voltage high, have extended cycle life, the advantage such as memory-less effect, have absolute advantages as electrokinetic cell.
Positive electrode material is as the key component of lithium ion battery, and at present, main positive electrode has cobalt acid lithium, mangaic acid
Lithium, LiFePO4 and ternary material etc..But, cobalt acid lithium is expensive, LiMn2O4 poor heat stability, LiFePO4 capacity low and
Low temperature properties is poor, ternary material poor stability.And phosphoric acid vanadium lithium is as positive electrode, there is higher voltage platform and higher reason
Opinion specific capacity, and heat stability is high, therefore, becomes a kind of important anode material for lithium-ion batteries.
At present, the main preparation methods of the persursor material vanadium phosphate of phosphoric acid vanadium lithium is high temperature solid-state method, carbothermic method
And sol-gel process.The common ground of these methods is to be required for reduction to have virose pentavalent vanadium source compound, and all also exists
Complex steps and operation complexity, be unfavorable for industrialized production.A kind of method that the invention provides simplicity is used to prepare lithium battery
Anode material vanadium lithium phosphate.
Summary of the invention
It is an object of the invention to solve at least one in the problems referred to above that prior art exists.
An object of the present invention be eliminate use virose pentavalent vanadium source to prepare vanadium phosphate, simplification prepare lithium from
The operating procedure of sub-battery positive pole material phosphoric acid vanadium lithium.
To achieve these goals, the invention provides a kind of side preparing cathode material lithium vanadium phosphate of lithium ion battery
Method, said method comprising the steps of:
Trivalent vanadium source compound and alkali reaction, obtain vanadium hydroxide, and wherein, described trivalent vanadium source compound can be sulphuric acid
Vanadium and/or vanadium chloride；
Vanadium hydroxide reacts with phosphoric acid solution, obtains vanadium phosphate.
Vanadium phosphate mixes with Lithium hydrate or lithium carbonate, sintering, obtains cathode material lithium vanadium phosphate of lithium ion battery.
In one exemplary embodiment of the present invention, described alkali can be sodium hydroxide, potassium hydroxide, calcium hydroxide,
One or more combination in ammonia.
In one exemplary embodiment of the present invention, described in obtain the step of vanadium hydroxide and include: by trivalent vanadium source
Compound is dissolved in water, and with alkali regulation pH value to 4～9, obtains vanadium hydroxide precipitation.
In one exemplary embodiment of the present invention, described in obtain the step of vanadium phosphate and include: dissolve with phosphoric acid solution
The precipitation of vanadium hydroxide, and be passed through noble gas and be heated to reflux, obtain vanadium phosphate.
In one exemplary embodiment of the present invention, described in the temperature that is heated to reflux be 80 DEG C～150 DEG C.
In one exemplary embodiment of the present invention, the consumption of described phosphate aqueous solution may be such that vanadium hydroxide is complete
1.03～1.5 times of the theoretical amount of full response.
In one exemplary embodiment of the present invention, the mol ratio that described vanadium phosphate mixes with Lithium hydrate or lithium carbonate
nLi:nvCan be 1.5～3.
In one exemplary embodiment of the present invention, described sintering step can be carried out under the protection of noble gas.
Compared with prior art, the Advantageous Effects of the application includes:
1, the present invention utilizes the Sulfovanadic acid of trivalent vanadium or vanadium chloride to carry out preparing phosphoric acid vanadium, instead of use tool virose five
Valency vanadium source compound so that technique more environmental protection；
2, the step of reduction pentavalent vanadium source compound is eliminated during the present invention prepares vanadium phosphate so that technological process is contracted
Short and simple to operate, it is easy to industrialized production.
Detailed description of the invention
Hereinafter, lithium ion cell positive material is prepared combining exemplary embodiment to the one describing the present invention in detail
The method of material phosphoric acid vanadium lithium.
A kind of method preparing cathode material lithium vanadium phosphate of lithium ion battery of the present invention comprises the following steps:
First, make trivalent vanadium source compound and alkali reaction, thus obtain vanadium hydroxide.Wherein, trivalent vanadium source compound can
Think Sulfovanadic acid (V2(SO4)3) and/or vanadium chloride (V3Cl2).And the alkali used can be sodium hydroxide, potassium hydroxide, hydroxide
One or more combination in calcium, ammonia.As long as the addition of alkali can make the pH value of the aqueous solution of Sulfovanadic acid or vanadium chloride
Be 4～9 with produce vanadium hydroxide precipitate.Vanadium hydroxide precipitation can also be collected.Can be come by filtration or centrifugation
Collection vanadium hydroxide precipitates.The vanadium hydroxide of collection can also be washed.Can be organic with water or such as methanol, ethanol, acetone etc.
One or more combination washing vanadium hydroxide in solvent.
Secondly, make vanadium hydroxide react with phosphoric acid solution, obtain vanadium phosphate.Here, vanadium hydroxide is permissible with phosphoric acid solution
Carrying out being heated to reflux processing, wherein, heating-up temperature can be 80 DEG C～150 DEG C, and the time of being heated to reflux can be 4h～10h, excellent
The heating-up temperature of choosing can be 100 DEG C～120 DEG C, and the time of being heated to reflux can be 6h～8h.The process of being heated to reflux can use
Oil bath mode of heating can also use heating in water bath mode.The process of being heated to reflux can be carried out in an inert atmosphere, wherein,
Noble gas can be one or more the combination in nitrogen, argon, helium.
In the method preparing vanadium phosphate, it is also possible to collect vanadium phosphate precipitation.This process can be by filtering or centrifugal point
From collecting vanadium phosphate precipitation.The vanadium phosphate of collection can also be washed.Can having with water or such as methanol, ethanol, acetone etc.
One or more combination washing vanadium phosphate precipitation in machine solvent.Washed vanadium phosphate can also be dried.Can be
Being dried process under vacuum condition, baking temperature can be 50 DEG C～70 DEG C, and drying time can be 2h～10h.
Finally, make vanadium phosphate and Lithium hydrate or the lithium carbonate can be according to mol ratio nLi:nvIt is 1.5～3 mixing, then lazy
Property atmosphere under sinter 5h～12h, obtain cathode material lithium vanadium phosphate of lithium ion battery.Wherein, vanadium phosphate and Lithium hydrate or carbon
After acid lithium mixing, can be through ball-milling treatment, wherein, Ball-milling Time can be 1h～3h.The noble gas used can be nitrogen
One or more combination in gas, argon, helium, preferably argon.Wherein, noble gas can be nitrogen, argon,
One or more combination in helium.
The exemplary embodiment of the present invention is described in further detail below in conjunction with concrete example.
Embodiment 1
Weigh 0.1mol (39g) Sulfovanadic acid (V2(SO4)3), add in 200mL deionized water, ultrasonic dissolution, obtain containing three
The solution A of valency vanadium ion.
With sodium hydroxide solution (concentration is 20wt%), the pH value of solution A is adjusted to 6, solution A produces a large amount of precipitate B.
Precipitate B is dissolved in the phosphoric acid solution of 200mL, under the protection of argon after 100 DEG C of backflow 6h, is precipitated C, mistake
Filter washing precipitate C.
By precipitate C 60 DEG C of dry 2h under vacuum, obtain vanadium phosphate (VPO4) solid.
Prepared vanadium phosphate and lithium carbonate are mixed equal to 2.5 in molar ratio, after ball milling 2h, under the protection of argon 500
DEG C sintering 8h, obtain vanadium phosphate cathode material M1.
As positive electrode material, M1 is assembled lithium ion battery test, and high specific capacity reaches 120mAh/g (0.5C times
Rate is discharged).
Embodiment 2
Weigh 0.1mol (15.75g) vanadium trichloride (VCl3), add in 200mL deionized water, ultrasonic dissolution, contained
The solution A of trivalent vanadium ion.
With ammonia (concentration is 20wt%), the pH value of solution A is adjusted to 7, solution A produces a large amount of precipitate B.
Precipitate B is dissolved in the phosphoric acid solution of 200mL, under the protection of argon after 120 DEG C of backflow 4h, is precipitated C, mistake
Filter washing precipitate C.
By precipitate C 50 DEG C of dry 3h under vacuum, obtain vanadium phosphate (VPO4) solid.
Prepared vanadium phosphate and lithium carbonate are mixed equal to 2.5 in molar ratio, after ball milling 2h, under the protection of argon 500
DEG C sintering 8h, obtain vanadium phosphate cathode material M2.
As positive electrode material, M2 is assembled lithium ion battery test, and high specific capacity reaches 125mAh/g (0.5C times
Rate is discharged).
In sum, the present invention utilizes the Sulfovanadic acid of trivalent vanadium or vanadium chloride to carry out preparing phosphoric acid vanadium, instead of use and has
The pentavalent vanadium source compound of toxicity so that technique more environmental protection；The present invention eliminates reduction five during preparing vanadium phosphate
The step of valency vanadium source compound so that technological process is shortened, and simple to operate, it is easy to industrialized production.
Although describing the present invention already in connection with exemplary embodiment above, but those of ordinary skill in the art should be clear
Chu, in the case of without departing from spirit and scope by the claims, can carry out various amendment to above-described embodiment.
Claims (8)
1. the method preparing cathode material lithium vanadium phosphate of lithium ion battery, it is characterised in that described method includes following step
Rapid:
Trivalent vanadium source compound and alkali reaction, obtain vanadium hydroxide, and wherein, trivalent vanadium source compound is Sulfovanadic acid and/or chlorination
Vanadium；
Vanadium hydroxide reacts with phosphoric acid solution, obtains vanadium phosphate；
Vanadium phosphate mixes with Lithium hydrate or lithium carbonate, sintering, obtains cathode material lithium vanadium phosphate of lithium ion battery.
The method preparing cathode material lithium vanadium phosphate of lithium ion battery the most according to claim 1, it is characterised in that described
Alkali is one or more the combination in sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia.
The method preparing cathode material lithium vanadium phosphate of lithium ion battery the most according to claim 1, it is characterised in that described
The step obtaining vanadium hydroxide includes: trivalent vanadium source compound is dissolved in water, and with alkali regulation pH value to 4～9, obtains hydroxide
Vanadium precipitates.
The method preparing cathode material lithium vanadium phosphate of lithium ion battery the most according to claim 1, it is characterised in that described
The step obtaining vanadium phosphate includes: by the precipitation of phosphoric acid solution dissolved hydrogen vanadium oxide, and is passed through noble gas and is heated to reflux,
Obtain vanadium phosphate.
The method preparing cathode material lithium vanadium phosphate of lithium ion battery the most according to claim 4, it is characterised in that described
The temperature being heated to reflux is 80 DEG C～150 DEG C.
The method preparing cathode material lithium vanadium phosphate of lithium ion battery the most according to claim 1, it is characterised in that described
The consumption of phosphoric acid solution is so that 1.03～1.5 times of the theoretical amount that vanadium hydroxide reacts completely.
The method preparing cathode material lithium vanadium phosphate of lithium ion battery the most according to claim 1, it is characterised in that described
Mol ratio n that vanadium phosphate mixes with sodium phosphate or sodium carbonateLi:nv=1.5～3.
The method preparing cathode material lithium vanadium phosphate of lithium ion battery the most according to claim 1, it is characterised in that described
Sintering step is carried out under the protection of noble gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610993929.8A CN106328943A (en) | 2016-11-11 | 2016-11-11 | Method for preparing lithium vanadium phosphate (positive electrode material) of lithium ion cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610993929.8A CN106328943A (en) | 2016-11-11 | 2016-11-11 | Method for preparing lithium vanadium phosphate (positive electrode material) of lithium ion cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106328943A true CN106328943A (en) | 2017-01-11 |
Family
ID=57817038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610993929.8A Pending CN106328943A (en) | 2016-11-11 | 2016-11-11 | Method for preparing lithium vanadium phosphate (positive electrode material) of lithium ion cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106328943A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108461751A (en) * | 2018-03-31 | 2018-08-28 | 广东天劲新能源科技股份有限公司 | A kind of preparation method of mesoporous vanadium phosphate cathode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101627493A (en) * | 2007-03-06 | 2010-01-13 | 威伦斯技术公司 | Method of making active materials for use in secondary electrochemical cells |
| CN102774821A (en) * | 2012-07-30 | 2012-11-14 | 四川大学 | Solid phase-hydrothermal preparation method for lithium vanadium phosphate |
| WO2015178479A1 (en) * | 2014-05-23 | 2015-11-26 | 国立大学法人東京農工大学 | Positive electrode material, secondary battery, method for manufacturing positive electrode material, and method for manufacturing secondary battery |
| CN105932277A (en) * | 2016-03-01 | 2016-09-07 | 马鞍山宇驰新能源材料有限公司 | Preparation method of three-dimensional porous vanadium phosphate sodium / carbon anode material |
-
2016
- 2016-11-11 CN CN201610993929.8A patent/CN106328943A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101627493A (en) * | 2007-03-06 | 2010-01-13 | 威伦斯技术公司 | Method of making active materials for use in secondary electrochemical cells |
| CN102774821A (en) * | 2012-07-30 | 2012-11-14 | 四川大学 | Solid phase-hydrothermal preparation method for lithium vanadium phosphate |
| WO2015178479A1 (en) * | 2014-05-23 | 2015-11-26 | 国立大学法人東京農工大学 | Positive electrode material, secondary battery, method for manufacturing positive electrode material, and method for manufacturing secondary battery |
| CN105932277A (en) * | 2016-03-01 | 2016-09-07 | 马鞍山宇驰新能源材料有限公司 | Preparation method of three-dimensional porous vanadium phosphate sodium / carbon anode material |
Non-Patent Citations (1)
| Title |
|---|
| 汪多仁: "《精细化工品实用生产技术手册:增塑剂化学品生产配方和合成工艺 第1版》", 31 August 1999, 科学技术文献出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108461751A (en) * | 2018-03-31 | 2018-08-28 | 广东天劲新能源科技股份有限公司 | A kind of preparation method of mesoporous vanadium phosphate cathode material |
| CN108461751B (en) * | 2018-03-31 | 2022-10-11 | 广东天劲新能源科技股份有限公司 | Preparation method of mesoporous lithium vanadium phosphate cathode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108666537B (en) | Lithium-sulfur battery composite positive electrode material, preparation method thereof and application of lithium-sulfur battery | |
| CN111270072B (en) | Recycling method of waste lithium iron phosphate battery positive electrode material | |
| CN101339992B (en) | Preparation of lithium ionic cell positive electrode material vanadium lithium silicate | |
| CN102464309B (en) | Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide | |
| CN112028123B (en) | Preparation method of manganese vanadate material and energy storage application thereof | |
| CN104362343A (en) | Preparation method and application of one-dimensional rod-like CuFeS2 compound | |
| CN108615874A (en) | A kind of kalium ion battery positive electrode and preparation method thereof based on nickel manganese binary oxide | |
| CN106410193A (en) | Method for preparing vanadium sodium phosphate and vanadium phosphate serving as anode material of sodium ion battery | |
| CN102769138A (en) | Method for synthesizing manganese phosphate lithium sol-gel doped with other metal ions | |
| CN109192963A (en) | Lithium ferric manganese phosphate composite material and lithium ion battery | |
| CN107123810A (en) | A kind of preparation method and applications based on nickel phosphide skeleton structure composite | |
| CN104362319A (en) | Preparation method of porous tin-carbon composite negative material | |
| CN107046128A (en) | A kind of preparation method of iron manganese phosphate for lithium composite | |
| CN113526551B (en) | Method for preparing mixed-phase vanadium dioxide heterojunction through segmented solvothermal reaction and application | |
| CN112777611B (en) | Rhombohedral phase Prussian blue derivative and preparation method and application thereof | |
| CN109473638A (en) | A kind of fluorine-containing electrode material Na of carbon coating3V2O2x(PO4)2F3-2xAnd preparation method thereof | |
| CN105118968A (en) | Nested V2O3-cladding lithium vanadium phosphate lithium ion anode material | |
| CN106328943A (en) | Method for preparing lithium vanadium phosphate (positive electrode material) of lithium ion cell | |
| CN108269983A (en) | Carbon-coated manganese oxide negative electrode material and preparation method thereof | |
| CN105375029A (en) | Ternary silicate composite cathode material and preparation method therefor | |
| Su et al. | Co-substitution in a Prussian blue analog with a hollow heterostructure for ultrahigh capacity and rate capability aqueous Zn 2+ batteries | |
| CN102544512A (en) | Ferrous silicate lithium anode material with vanadates doped at anion positions and preparation method thereof | |
| CN106495122A (en) | A kind of method that waste lithium iron phosphate positive plate reclaims iron phosphate presoma | |
| CN116845408A (en) | Method for recycling waste lithium cobaltate battery positive electrode material by using water-based eutectic solvent | |
| CN113955735B (en) | Method for preparing hydroxyl phosphate and lithium-containing phosphate by air oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170111 |