CN104183846A - Lithium manganese phosphate nanoparticles and preparation method thereof - Google Patents
Lithium manganese phosphate nanoparticles and preparation method thereof Download PDFInfo
- Publication number
- CN104183846A CN104183846A CN201410413620.8A CN201410413620A CN104183846A CN 104183846 A CN104183846 A CN 104183846A CN 201410413620 A CN201410413620 A CN 201410413620A CN 104183846 A CN104183846 A CN 104183846A
- Authority
- CN
- China
- Prior art keywords
- mol
- lithium
- concentration
- manganese phosphate
- lithium manganese
- 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.)
- Granted
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses lithium manganese phosphate nanoparticles. The nanoparticles have the size of 5-50nm. A preparation method of the nanoparticles comprises the steps that a solvent, required for water/solvent thermal reaction, is prepared from ethylene glycol and water, manganese acetate tetrahydrate, lithium acetate dihydrate and phosphoric acid are taken as reacting materials, P123 is taken as a surfactant, potassium hydroxide is taken as a mineralizer, so as to promote nucleation and growth, heat treatment is carried out at high temperature and high pressure, then, segmented calcining is carried out at the temperature of 300-400 DEG C and 550-650 DEG C under the protection of a nitrogen or argon atmosphere, and then, the lithium manganese phosphate nanoparticles are obtained. The lithium manganese phosphate nanoparticles and the preparation method thereof have the advantages that the product is stable in quality, high in purity and good in particle dispersibility and is beneficial to the diffusion of lithium ions and the improvement of the electrochemical properties of a lithium-ion battery, and the preparation process is simple in process, easy to control and low in cost and is pollution-free, so that the large-scale production is facilitated.
Description
Technical field
The present invention relates to a kind of lithium manganese phosphate nano material and preparation method thereof, relate in particular to a kind of lithium manganese phosphate nano particle and preparation method thereof.
Background technology
Lithium ion battery is as a kind of high performance green power supply of filling, in various portable type electronic products and communication tool, be used widely in recent years, and be progressively developed as the electrical source of power of electric automobile, thereby promote it to the future development of safety, environmental protection, low cost and high-energy-density.Wherein, particularly the development of positive electrode is very crucial for new electrode materials.The anode material for lithium-ion batteries of broad research concentrates on the transition metal oxide of lithium as the LiMO of layer structure at present
2the LiMn of (M=Co, Ni, Mn) and spinel structure
2o
4.But they respectively have shortcoming, LiCoO as positive electrode
2cost is high, natural resources shortage, and toxicity is large; Lithium nickelate (LiNiO
2) preparation difficulty, poor heat stability; LiMn
2o
4capacity is lower, and cyclical stability especially high-temperature behavior is poor.In order to solve the defect of above material, people have done large quantity research, above positive electrode are being carried out to various modifications with when improving its performance, and the exploitation of novel anode material is also the emphasis of paying close attention to always.Research is found, lithium manganese phosphate material operating voltage moderate (4.1V), the high 171mAh/g of theoretical capacity, good cycle, cost is very low, and his energy density is higher by 34% than LiFePO4, and its high-energy-density and high safety performance make it in power lithium-ion battery, have outstanding application prospect, weak point is that its poorly conductive and lithium ion diffusion velocity is slow, and the particle size of this and manganese-lithium phosphate anode material has great associated.The present invention utilizes simple method to prepare the manganese-lithium phosphate anode material of the favorable dispersibility that size is less, is conducive to improve battery performance.
summary of the invention
The object of the present invention is to provide simple lithium manganese phosphate nano particle of a kind of favorable dispersibility and preparation technology and preparation method thereof.
Lithium manganese phosphate nano particle of the present invention, granular size is 5-50 nanometer.
The method of preparing above-mentioned lithium manganese phosphate nano particle, step is as follows:
1) by P123(poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer PEO-PPO-PEO) be dissolved in deionized water, stir at least 240 minutes, add again four hydration manganese acetate and ascorbic acid, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.4 mol/L-1.0 mol/L, ascorbic acid concentrations are 0.076 mol/L-0.152 mol/L, and P123 concentration is the solution A of 0.13-0.26 g/mL;
2) take phosphoric acid, two hydration lithium acetates are dissolved in ethylene glycol, stir more than 30 minutes, forming phosphoric acid concentration is 0.4 mol/L-1.0 mol/L, the concentration of lithium acetate is the suspension B of 0.4 mol/L-3.0 mol/L;
3) by step 2) suspension B under the state stirring, be added drop-wise to step 1) solution A in, form emulsion C, in emulsion C, the mol ratio of Li, Mn, P is 1 ~ 3:1:1;
4) the emulsion C of step 3) is transferred to autoclave, the ethylene glycol solution that adds KOH, fully stir, spent glycol regulates its volume to 2/3 ~ 4/5 of reactor volume again, making KOH concentration is 0.05-0.15 mol/L, the concentration of P is 0.15 mol/L-0.375 mol/L, stirs more than 30 minutes;
5) reactor is airtight; be incubated 4-48 hour at 160-230 ℃ after, heat-treat, then, be down to room temperature; take out product; filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 40～100 ℃ of temperature, dry; again under nitrogen or argon shield; after 300 ~ 400 ℃ of calcining 3h, at 650 ℃ of calcining 4h of 550-, obtain lithium manganese phosphate nano particle.
In said method, the purity of raw material phosphoric acid, four hydration manganese acetates, two hydration lithium acetates, ascorbic acid, potassium hydroxide, P123 and solvent ethylene glycol used, deionized water, acetone is all not less than chemical pure.
It is reaction mass that four hydration manganese acetates, two hydration lithium acetates, phosphoric acid are take in the present invention, P123 is surfactant, potassium hydroxide is mineralizer, ethylene glycol and deionized water are reaction dissolvent, by adding the concentration of P123 surfactant and design mineralizer potassium hydroxide, forming core and the growth course of lithium manganese phosphate in regulation and control heat treatment process, realize single water/solvent heat of lithium manganese phosphate nano particle that disperses synthetic.The present invention is for the organic substance of reaction mass introducing is fully separated with synthetic lithium manganese phosphate with mineralizer KOH to the cleaning of water/solvent heat synthetic product, obtains the lithium manganese phosphate phase of pure phase.Employing absolute ethyl alcohol dewaters and not higher than the oven dry of 100 ℃, is in order to obtain lithium manganese phosphate nano-powder.Under nitrogen or argon gas atmosphere protection, carry out calcination processing, be for P123 being removed, obtaining lithium manganese phosphate nano particle.
Constant product quality of the present invention, purity is high, and particle dispersion is good, is conducive to lithium ion diffusion, improves the large current density performance of lithium ion battery.Preparation process of the present invention is simple, is easy to control, and pollution-free, cost is low, is easy to large-scale production.
Accompanying drawing explanation
X-ray diffraction (XRD) collection of illustrative plates of Fig. 1 lithium manganese phosphate nano particle;
Scanning electron microscopy (SEM) picture of Fig. 2 lithium manganese phosphate nano particle.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Example 1
1) 2.000 g P123 are dissolved in to the deionized water of 15 ml, stir 240 minutes, add again the four hydration manganese acetates of 1.470g and the ascorbic acid of 0.200g, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.4 mol/L, ascorbic acid concentrations are 0.076 mol/L, and P123 concentration is the solution A of 0.13 g/mL;
2) take the phosphoric acid of 0.588g, the two hydration lithium acetates of 0.612g are dissolved in the ethylene glycol of 15 ml, stir 30 minutes, forming phosphoric acid concentration is 0.4 mol/L, and the concentration of lithium acetate is the suspension B of 0.4 mol/L;
3) by step 2) prepared suspension B is added drop-wise to step 1 under the state stirring) in prepared solution A, form emulsion C.In emulsion C, the mol ratio of Li, Mn, P is 1:1:1.
4) the emulsion C of step 3) is transferred to the autoclave that volume is 60ml, the ethylene glycol solution that adds 5 ml to contain 0.112 g KOH, fully stirs, spent glycol regulates its volume to 40ml again, making KOH concentration is 0.05 mol/L, and the concentration of P is 0.15 mol/L, stirs 30 minutes;
5) reactor that disposes reaction mass in step 4) is airtight, at 230 ℃, be incubated after 12 hours.Take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 100 ℃ of temperature, dry.Under nitrogen or argon shield, after 300 ℃ of calcining 3h, at 550 ℃ of calcining 4h, obtain lithium manganese phosphate nano particle again.
The X-ray diffraction that obtains lithium manganese phosphate nanometer ellipsoid (XRD) collection of illustrative plates of synthesized is shown in Fig. 1, the lithium manganese phosphate that visible prepared material is pure phase; Its scanning electron microscopy (SEM) photo is shown in Fig. 2, visible synthetic lithium manganese phosphate nano particle, and size is 5-50 nanometer.
Example 2
1) 3.000 g P123 are dissolved in to the deionized water of 15 ml, stir 300 minutes, add again the four hydration manganese acetates of 2.45g and the ascorbic acid of 0.400g, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.67 mol/L, ascorbic acid concentrations are 0.152 mol/L, and P123 concentration is the solution A of 0.20 g/mL;
2) take the phosphoric acid of 0.98g, the two hydration lithium acetates of 2.04g are dissolved in the ethylene glycol of 15 ml, stir 90 minutes, forming phosphoric acid concentration is 0.67 mol/L, and the concentration of lithium acetate is the suspension B of 1.33 mol/L;
3) by step 2) prepared suspension B is added drop-wise to step 1 under the state stirring) in prepared solution A, form emulsion C.In emulsion C, the mol ratio of Li, Mn, P is 2:1:1.
4) the emulsion C of step 3) is transferred to the autoclave that volume is 50ml, the ethylene glycol solution that adds 5 ml to contain 0.224 g KOH, fully stirs, spent glycol regulates its volume to 40ml again, making KOH concentration is 0.10 mol/L, and the concentration of P is 0.25 mol/L, stirs 90 minutes;
5) reactor that disposes reaction mass in step 4) is airtight, at 200 ℃, be incubated after 24 hours.Take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 80 ℃ of temperature, dry.Under nitrogen or argon shield, after 350 ℃ of calcining 3h, at 600 ℃ of calcining 4h, obtain lithium manganese phosphate nano particle again, size is 5-50 nanometer.
Example 3
1) 3.500 g P123 are dissolved in to the deionized water of 15 ml, stir 360 minutes, add again the four hydration manganese acetates of 2.94g and the ascorbic acid of 0.240g, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.80 mol/L, ascorbic acid concentrations are 0.091 mol/L, and P123 concentration is the solution A of 0.23 g/mL;
2) take the phosphoric acid of 1.176g, the two hydration lithium acetates of 1.224g are dissolved in the ethylene glycol of 15 ml, stir 150 minutes, forming phosphoric acid concentration is 0.80 mol/L, and the concentration of lithium acetate is the suspension B of 0.80 mol/L;
3) by step 2) prepared suspension B is added drop-wise to step 1 under the state stirring) in prepared solution A, form emulsion C.In emulsion C, the mol ratio of Li, Mn, P is 1:1:1.
4) the emulsion C of step 3) is transferred to the autoclave that volume is 55ml, the ethylene glycol solution that adds 8 ml to contain 0.336 g KOH, fully stirs, spent glycol regulates its volume to 40ml again, making KOH concentration is 0.15 mol/L, and the concentration of P is 0.3 mol/L, stirs 150 minutes;
5) reactor that disposes reaction mass in step 4) is airtight, at 180 ℃, be incubated after 30 hours.Take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 80 ℃ of temperature, dry.Under nitrogen or argon shield, after 300 ℃ of calcining 3h, at 650 ℃ of calcining 4h, obtain lithium manganese phosphate nano particle again, size is 5-50 nanometer.
Example 4
1) 4.000 g P123 are dissolved in to the deionized water of 15 ml, stir 400 minutes, add again the four hydration manganese acetates of 3.675g and the ascorbic acid of 0.320g, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 1.00 mol/L, ascorbic acid concentrations are 0.12 mol/L, and P123 concentration is the solution A of 0.26 g/mL;
2) take the phosphoric acid of 1.470 g, the two hydration lithium acetates of 4.590 g are dissolved in the ethylene glycol of 15 ml, stir 200 minutes, forming phosphoric acid concentration is 1.00 mol/L, and the concentration of lithium acetate is the suspension B of 3.00 mol/L;
3) by step 2) prepared suspension B is added drop-wise to step 1 under the state stirring) in prepared solution A, form emulsion C.In emulsion C, the mol ratio of Li, Mn, P is 3:1:1.
4) the emulsion C of step 3) is transferred to the autoclave that volume is 50ml, the ethylene glycol solution that adds 5 ml to contain 0.112 g KOH, fully stirs, spent glycol regulates its volume to 40ml again, making KOH concentration is 0.05 mol/L, and the concentration of P is 0.375 mol/L, stirs 200 minutes;
5) reactor that disposes reaction mass in step 4) is airtight, at 160 ℃, be incubated after 48 hours.Take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 40 ℃ of temperature, dry.Under nitrogen or argon shield, after 400 ℃ of calcining 3h, at 600 ℃ of calcining 4h, obtain lithium manganese phosphate nano particle again, size is 5-50 nanometer.
Claims (3)
1. a lithium manganese phosphate nano particle, is characterized in that described nano particle size is 5-50 nanometer.
2. prepare the method for lithium manganese phosphate nano particle as claimed in claim 1, it is characterized in that step is as follows:
1) P123 is dissolved in to deionized water, stir at least 240 minutes, add again four hydration manganese acetate and ascorbic acid, be stirred to abundant dissolving, obtaining manganese acetate concentration is that 0.4 mol/L-1.0 mol/L, ascorbic acid concentrations are 0.076 mol/L-0.152 mol/L, and P123 concentration is the solution A of 0.13-0.26 g/mL;
2) take phosphoric acid, two hydration lithium acetates are dissolved in ethylene glycol, stir more than 30 minutes, forming phosphoric acid concentration is 0.4 mol/L-1.0 mol/L, the concentration of lithium acetate is the suspension B of 0.4 mol/L-3.0 mol/L;
3) by step 2) suspension B under the state stirring, be added drop-wise to step 1) solution A in, form emulsion C, in emulsion C, the mol ratio of Li, Mn, P is 1 ~ 3:1:1;
4) the emulsion C of step 3) is transferred to autoclave, the ethylene glycol solution that adds KOH, fully stir, spent glycol regulates its volume to 2/3 ~ 4/5 of reactor volume again, making KOH concentration is 0.05-0.15 mol/L, the concentration of P is 0.15 mol/L-0.375 mol/L, stirs more than 30 minutes;
5) reactor is airtight; be incubated 4-48 hour at 160-230 ℃ after, heat-treat, then, be down to room temperature; take out product; filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 40～100 ℃ of temperature, dry; again under nitrogen or argon shield; after 300 ~ 400 ℃ of calcining 3h, at 650 ℃ of calcining 4h of 550-, obtain lithium manganese phosphate nanometer rods.
3. the preparation method of lithium manganese phosphate nano particle according to claim 2, is characterized in that the purity of raw material phosphoric acid used, four hydration manganese acetates, two hydration lithium acetates, ascorbic acid, potassium hydroxide, P123 and solvent ethylene glycol, deionized water, acetone is all not less than chemical pure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410413620.8A CN104183846B (en) | 2014-08-21 | 2014-08-21 | A kind of lithium manganese phosphate nano particle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410413620.8A CN104183846B (en) | 2014-08-21 | 2014-08-21 | A kind of lithium manganese phosphate nano particle and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104183846A true CN104183846A (en) | 2014-12-03 |
| CN104183846B CN104183846B (en) | 2016-04-27 |
Family
ID=51964726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410413620.8A Expired - Fee Related CN104183846B (en) | 2014-08-21 | 2014-08-21 | A kind of lithium manganese phosphate nano particle and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104183846B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112635758A (en) * | 2020-10-23 | 2021-04-09 | 珠海鹏辉能源有限公司 | Preferentially oriented nano lithium manganese phosphate or composite material thereof, preparation method thereof, lithium ion battery anode material and lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009544563A (en) * | 2006-12-22 | 2009-12-17 | ユミコア ソシエテ アノニム | Synthesis of electroactive crystalline nanometric LiMnPO4 powder |
| CN102956887A (en) * | 2012-11-14 | 2013-03-06 | 佛山市德方纳米科技有限公司 | Preparation method of nano-grade lithium manganese phosphate anode material |
| CN103996853A (en) * | 2014-05-28 | 2014-08-20 | 天津大学 | Method for preparing nano lithium manganese phosphate material with uniform size |
-
2014
- 2014-08-21 CN CN201410413620.8A patent/CN104183846B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009544563A (en) * | 2006-12-22 | 2009-12-17 | ユミコア ソシエテ アノニム | Synthesis of electroactive crystalline nanometric LiMnPO4 powder |
| CN102956887A (en) * | 2012-11-14 | 2013-03-06 | 佛山市德方纳米科技有限公司 | Preparation method of nano-grade lithium manganese phosphate anode material |
| CN103996853A (en) * | 2014-05-28 | 2014-08-20 | 天津大学 | Method for preparing nano lithium manganese phosphate material with uniform size |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112635758A (en) * | 2020-10-23 | 2021-04-09 | 珠海鹏辉能源有限公司 | Preferentially oriented nano lithium manganese phosphate or composite material thereof, preparation method thereof, lithium ion battery anode material and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104183846B (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106450195B (en) | A kind of positive material for lithium-sulfur battery and preparation method thereof and the lithium-sulfur cell containing the positive electrode | |
| CN111082058B (en) | Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof | |
| CN103066280A (en) | Spherical lithium iron phosphate anode material and preparation method thereof | |
| CN101891181B (en) | Preparation method of pure-phase high-crystallinity lithium iron phosphate | |
| CN102838102B (en) | Preparation method of lithium iron phosphate monocrystalline nanorods | |
| CN104183827B (en) | A kind of lithium iron phosphate nano rod and preparation method thereof | |
| CN114864896A (en) | In-situ carbon-coated nano lithium iron phosphate cathode material and preparation method thereof | |
| CN103996852A (en) | Preparation method of novel nano lithium vanadium phosphate positive electrode material | |
| CN103833083B (en) | The preparation method of a kind of LiFePO4-phosphoric acid vanadium lithium composite material precursor | |
| CN102903918B (en) | Preparation method for manganese phosphate lithium nanosheet | |
| CN104037412A (en) | Preparation method of multilevel-structured hollow nano-sphere of negative electrode material of high-performance lithium ion secondary battery | |
| CN113845152A (en) | Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery | |
| CN115763766A (en) | Na 2 MnPO 4 F-coated O3 type layered sodium-ion battery positive electrode material and preparation method thereof | |
| CN103050681A (en) | Preparation method of high-compaction spherical ternary cathode material | |
| CN105047898A (en) | Twin-spherical lithium-rich cathode material of lithium ion secondary battery and preparation method thereof | |
| CN112777611B (en) | Rhombohedral phase Prussian blue derivative and preparation method and application thereof | |
| CN106410185A (en) | Preparation method for lithium ion battery manganese-based cathode materials of egg yolk-egg shell structure | |
| CN107445210B (en) | High-capacity iron-based lithium ion battery anode material α -LiFeO2Preparation method of (1) | |
| CN103296266B (en) | Zinc titanate lithium titanate cathode material of doped with Cu and preparation method thereof | |
| CN112624198A (en) | Method for synthesizing high-activity layered zinc ion secondary battery anode material by one-step method at room temperature | |
| CN104183845B (en) | A kind of lithium manganese phosphate nano particle and preparation method thereof | |
| CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery | |
| CN102723478A (en) | Octahedral lithium manganate micron single crystal electrode material and preparation method thereof | |
| CN116081710A (en) | Potassium-doped nickel-manganese-copper ternary layered oxide and preparation method and application thereof | |
| CN104183846B (en) | A kind of lithium manganese phosphate nano particle and preparation method 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 | ||
| C14 | Grant of patent or utility model | ||
| 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: 20160427 Termination date: 20190821 |