CN105185990B - A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one - Google Patents
A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one Download PDFInfo
- Publication number
- CN105185990B CN105185990B CN201510503366.5A CN201510503366A CN105185990B CN 105185990 B CN105185990 B CN 105185990B CN 201510503366 A CN201510503366 A CN 201510503366A CN 105185990 B CN105185990 B CN 105185990B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- lithium ion
- secondary battery
- ion secondary
- battery positive
- 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.)
- Expired - Fee Related
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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one, spherical lithium ion secondary battery positive electrode VPO is prepared using hydro-thermal method4·H2O, reaction condition is gentle, and product purity is high, better crystallinity degree, and mean particle size is 1.5 ~ 3 μm, particle diameter distribution is uniform, soilless sticking phenomenon；The positive electrode of preparation is regular spheric granules, and its structure has higher specific surface area, is advantageous to being sufficiently humidified so as to for electrolyte, is advantageous to transmission of the lithium ion inside it in charge and discharge process；The spherical lithium ion secondary battery positive electrode VPO that the present invention synthesizes4·H2O shows good chemical property.
Description
Technical field
The present invention relates to electrochemical field, specifically a kind of water vanadium phosphate of spherical lithium ion secondary battery positive electrode one
Preparation method.
Background technology
Lithium rechargeable battery is a kind of new Green Chemistry power supply, compared with traditional nickel-cadmium cell, Ni-MH battery
With the advantage such as voltage is high, long lifespan and energy density are big, small volume, self-discharge rate are low.From nineteen ninety for the first time enter market with
It is more and more wider to carry out use range, has been widely used in various portable electric appts.With the rise of new-energy automobile, lithium
Ion battery is with its excellent characteristic, it is considered to be one of preferable energy storage device of new-energy automobile.
Because in the composition of lithium rechargeable battery, positive electrode is to determine its chemical property, security performance, price
And the key factor of future thrust.At present, positive electrode is mostly lithium-transition metal composite oxides, and people have ground
The cobalt lithia of layer structure, the lithium manganese oxygen of spinel structure are studied carefully, also lithium ni-mh overcharges dangerous, and cobalt resource is tight at present
Lack；Lithium manganese oxygen capacity is low and has John Tail effects, have impact on its chemical property, high temperature cyclic performance is poor.Nickle cobalt lithium manganate
Ternary material is because resource shortage and the nickel of cobalt, cobalt are into the reason such as high and price fluctuation is big, it is difficult to turn into power used for electric vehicle
The main flow of type lithium ion battery, so needing to develop the secondary positive electrode of new type lithium ion to meet the development need of society.
China's navajoite aboundresources, reserves account for the 38.5% of the whole world, in the explored vanadium iron magnetic ore reserves in Panzhihua Region
About 10,000,000,000 tons, vanadium reserves account for the 62% of China.But navajoite exploitation is limited by correlation technique, if mutually tied with energy technology
Close, target is turned to industry, can not only develop and utilize new energy, but also the application field of vanadium resource can be expanded, greatly
Power lifts the comprehensive utilization value of vanadium resource.Therefore VPO4·H2O is a lithium rechargeable battery with very big potential value
Positive electrode, it is domestic at present not to be related to VPO4·H2O reports as the preparation of lithium ion secondary battery anode material.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one, comprises the following steps：
1）By H3PO4And VCl3It is 3 according to mol ratio：1~5：1 is added in ptfe autoclave, adds water stirring mixed
Close, adjust pH value while stirring to 1.5 ~ 3.5, then ptfe autoclave is sealed, stirs 45 ~ 50h；
2）Reactor is put into Muffle furnace heating heating is carried out with 5 DEG C/min speed, when being warming up to 150 ~ 200 DEG C, protected
70 ~ 75h of temperature；
3）Reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, by gained washing of precipitate, drying, i.e.,
Obtain target product VPO4·H2O；
The step 1）In to be used to adjust pH conditioning agent be methyl triethyl ammonium chloride；
The step 1）In mixing time be 48h；
The step 2）Middle soaking time is 72h；
The step 3）In be used for wash solvent be absolute ethyl alcohol；
The step 3）In drying temperature be 90 DEG C.
Beneficial effects of the present invention：
The preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one provided by the invention, utilizes hydro-thermal method
Prepare spherical lithium ion secondary battery positive electrode VPO4·H2O, reaction condition is gentle, and product purity is high, better crystallinity degree, particle
Average grain diameter is 1.5 ~ 3 μm, particle diameter distribution is uniform, soilless sticking phenomenon；The positive electrode of preparation is regular spheric granules, and it is tied
Structure has higher specific surface area, is advantageous to being sufficiently humidified so as to for electrolyte, is advantageous to lithium ion in charge and discharge process inside it
Transmission；The spherical lithium ion secondary battery positive electrode VPO that the present invention synthesizes4·H2O shows good chemical property.
Brief description of the drawings
Fig. 1 is spherical lithium ion secondary battery positive electrode VPO prepared by embodiment 14·H2O SEM figures one；
Fig. 2 is spherical lithium ion secondary battery positive electrode VPO prepared by embodiment 14·H2O SEM figures two；
Fig. 3 is spherical lithium ion secondary battery positive electrode VPO prepared by embodiment 14·H2O XRD；
Fig. 4 is spherical lithium ion secondary battery positive electrode VPO prepared by embodiment 14·H2O is in current density
0.09mA/cm2Under first charge-discharge curve.
Embodiment
With reference to embodiment, the present invention is further elaborated.
A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one, comprises the following steps：
1）By H3PO4And VCl3It is 3 according to mol ratio：1~5：1 is added in ptfe autoclave, adds water stirring mixed
Close, adjust pH value while stirring to 1.5 ~ 3.5, then ptfe autoclave is sealed, stirs 45 ~ 50h；
2）Reactor is put into Muffle furnace heating heating is carried out with 5 DEG C/min speed, when being warming up to 150 ~ 200 DEG C, protected
70 ~ 75h of temperature；
3）Reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, by gained washing of precipitate, drying, i.e.,
Obtain target product VPO4·H2O。
Embodiment 1
A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one, comprises the following steps：
1）By H3PO4And VCl3It is 4 according to mol ratio：1 is added in ptfe autoclave, adds water to be stirred,
PH value is adjusted to 2.5 with methyl triethyl ammonium chloride while stirring, and then ptfe autoclave is sealed, stirs 48h；
2）Reactor is put into Muffle furnace heating heating is carried out with 5 DEG C/min speed, when being warming up to 200 DEG C, insulation
72h；
3）Reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, gained precipitation is washed with absolute ethyl alcohol
Wash, then dried under the conditions of 90 DEG C, produce target product VPO4·H2O；
As shown in Figure 1 and Figure 2, for X-ray analysis as shown in figure 3, product is more pure, Fig. 4 is institute to the SEM figures of products therefrom
It is 0.09mA/cm that product, which is obtained, in current density2Under first charge-discharge curve, first discharge specific capacity is up to 62mAh/g.
Embodiment 2
A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one, comprises the following steps：
1）By H3PO4And VCl3It is 3 according to mol ratio：1 is added in ptfe autoclave, adds water to be stirred,
PH value is adjusted to 3.5 with methyl triethyl ammonium chloride while stirring, and then ptfe autoclave is sealed, stirs 45h；
2）Reactor is put into Muffle furnace heating heating is carried out with 5 DEG C/min speed, when being warming up to 150 DEG C, insulation
75h；
3）Reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, gained precipitation is washed with absolute ethyl alcohol
Wash, then dried under the conditions of 90 DEG C, produce target product VPO4·H2O。
Embodiment 3
A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one, comprises the following steps：
1）By H3PO4And VCl3It is 5 according to mol ratio：1 is added in ptfe autoclave, adds water to be stirred,
PH value is adjusted to 1.5 with methyl triethyl ammonium chloride while stirring, and then ptfe autoclave is sealed, stirs 50h；
2）Reactor is put into Muffle furnace heating heating is carried out with 5 DEG C/min speed, when being warming up to 180 DEG C, insulation
70h；
3）Reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, gained precipitation is washed with absolute ethyl alcohol
Wash, then dried under the conditions of 90 DEG C, produce target product VPO4·H2O。
Claims (4)
1. a kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one, it is characterised in that including following
Step：
1）By H3PO4And VCl3It is 4 according to mol ratio：1 is added in ptfe autoclave, adds water to be stirred, while stirring
Mix side and adjust pH value to 1.5 ~ 3.5, then ptfe autoclave is sealed, stirs 45 ~ 50h；
2）Reactor is put into Muffle furnace heating heating is carried out with 5 DEG C/min speed, when being warming up to 150 ~ 200 DEG C, insulation 70 ~
75h；
3）Reactor is down to room temperature with 5 DEG C/min speed, greenish precipitate is obtained, by gained washing of precipitate, drying, produces mesh
Mark product VPO4·H2O；Solvent for washing is absolute ethyl alcohol, and drying temperature is 90 DEG C.
2. the preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one as claimed in claim 1, its feature
It is：The step 1）In to be used to adjust pH conditioning agent be methyl triethyl ammonium chloride.
3. the preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one as claimed in claim 1, its feature
It is：The step 1）In mixing time be 48h.
4. the preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one as claimed in claim 1, its feature
It is：The step 2）Middle soaking time is 72h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510503366.5A CN105185990B (en) | 2015-08-17 | 2015-08-17 | A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510503366.5A CN105185990B (en) | 2015-08-17 | 2015-08-17 | A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105185990A CN105185990A (en) | 2015-12-23 |
| CN105185990B true CN105185990B (en) | 2018-01-02 |
Family
ID=54907941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510503366.5A Expired - Fee Related CN105185990B (en) | 2015-08-17 | 2015-08-17 | A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105185990B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102379563B1 (en) * | 2014-12-26 | 2022-03-28 | 삼성전자주식회사 | Composite positive active material, method for preparation thereof, positive electrode comprising the same and lithium battery comprising the positive electrode |
| CN107230771B (en) * | 2017-07-14 | 2020-08-14 | 中南大学 | Method for coating lithium ion battery cathode material nickel cobalt lithium manganate with vanadium phosphate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100424674B1 (en) * | 2001-05-19 | 2004-03-27 | 한국전자통신연구원 | Sonochemical preparation of VOPO4·2H2O and the use for cathode of rechargeable lithium battery |
| CN103872324B (en) * | 2014-03-28 | 2016-08-24 | 中南大学 | A kind of petal-shaped lithium ion battery negative material VPO4preparation method |
-
2015
- 2015-08-17 CN CN201510503366.5A patent/CN105185990B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105185990A (en) | 2015-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104218234B (en) | A kind of lithium ion battery composite cathode material of high circulation performance and preparation method thereof | |
| CN105742622A (en) | Olivine-structured LiMPO<4> surface modification layered lithium-rich manganese-based positive electrode material and preparation method therefor | |
| CN106450276B (en) | Lithium ion cell electrode modified material, preparation method and lithium ion battery | |
| CN104505505B (en) | The preparation method of the ternary layered positive electrode of Lithium metasilicate coated lithium ion battery | |
| CN106299282B (en) | Nitrogen-doped carbon nanotube sulfur composite material and preparation method thereof | |
| CN103413924B (en) | A kind of La 1-xca xcoO 3coated lithium ion battery LiNi 1/3co 1/3mn 1/3o 2positive electrode and preparation method thereof | |
| CN103682327B (en) | Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel | |
| CN104766959B (en) | A preparing method of a Li(Ni0.8Co0.1Mn0.1)O2 ternary material | |
| CN101308926B (en) | Lithium ionic cell composite positive pole material coated by orthosilicate and its preparation method | |
| CN103311532A (en) | Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure | |
| CN101944599B (en) | Preparation method of cobalt-based material | |
| CN106058238A (en) | Modified spherical nickel cobalt lithium manganate NCM622 anode material and preparation method thereof | |
| CN105826550A (en) | Preparation method of lithium manganate cathode material with ferri-containing compound coating | |
| CN102275890A (en) | Microwave-assisted synthesis method of nanometer lithium iron phosphate | |
| CN102185154A (en) | Nano ferric phosphate hollow sphere lithium ion battery and preparation method thereof | |
| CN106340621A (en) | Ferric negative electrode material for lithium battery and preparation method thereof | |
| CN105958039A (en) | Preparation method of modified lithium nickel manganese oxide cathode material, and high-voltage lithium ion battery | |
| CN103825014A (en) | Preparation method of lithium ion battery high-voltage cathode material lithium nickel manganese composite oxide | |
| CN103413935A (en) | Mo-doped lithium-rich positive electrode material and preparation method thereof | |
| CN105006563B (en) | Lithium ion battery anode active material Li2ZnTi3O8Preparation method | |
| CN105185990B (en) | A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one | |
| CN104241628A (en) | Method for preparing titanium-dioxide-modified ferric oxide microspheres as well as produced product and use of titanium-dioxide-modified ferric oxide microspheres | |
| CN104485443B (en) | A kind of graphene polymer coats the preparation method of niobium cation doping lithium aluminate composite positive pole | |
| CN107204424B (en) | Preparation method of lithium-rich manganese-based layered lithium battery positive electrode material | |
| CN101609880A (en) | A kind of ferrousphosphate lithium material of carbon coated and preparation technology thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180102 Termination date: 20190817 |