CN106981645A - Modified phosphate iron lithium anode material and preparation method thereof - Google Patents
Modified phosphate iron lithium anode material and preparation method thereof Download PDFInfo
- Publication number
- CN106981645A CN106981645A CN201710382828.1A CN201710382828A CN106981645A CN 106981645 A CN106981645 A CN 106981645A CN 201710382828 A CN201710382828 A CN 201710382828A CN 106981645 A CN106981645 A CN 106981645A
- Authority
- CN
- China
- Prior art keywords
- lithium
- iron
- source
- phosphate
- softening point
- 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
- H01M4/362—Composites
-
- 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
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation method of modified phosphate iron lithium anode material, including:(1)Lithium source, source of iron and carbon source mixture are crushed into obtain ferric lithium phosphate precursor;(2)By step(1)Obtained ferric lithium phosphate precursor is placed in the blast furnace of inert gas to heat up 500 DEG C~800 DEG C and sintered 8~16 hours, and cooling obtains changing surname lithium iron phosphate positive material.The carbon source is isotropism high softening point bitumen, and carbon content >=85%, softening point is 200~240 °C, toluene insolubles (TI):70~80 %, quinoline insolubles (QI) 25~35%.It will not be bonded together after the lithium iron phosphate particles sintering for the carbon source cladding that the present invention is used, it is not necessary to crushed, it is to avoid cause the breakage of carbon coating layer, obtained modified phosphate iron lithium has high discharge capacity, coulombic efficiency and long circulation life;Significantly reduce the discharge amount of exhaust gas in Material Manufacturing Process.
Description
Technical field
Isotropism high softening point bitumen is utilized the present invention relates to anode material for lithium-ion batteries technical field, more particularly to one kind
Modified phosphate iron lithium anode material and its method are prepared as carbon source.
Background technology
Lithium ion battery has a series of advantages such as specific capacity height, operating voltage height, the good, memory-less effect of security,
It is widely used in notebook computer, mobile phone and many portable electronic instrument equipment of instrument and meter lamp, meanwhile, electronic
Also there is good application prospect in the fields such as car automobile, electric tool and energy-accumulating power station.Therefore, with lithium ion battery applications field
Constantly widen and corresponding product continuous upgrading with regenerating, lithium ion battery will be proposed it is higher and higher require, and carry
The most direct method of high battery combination property is to improve battery material performance.Positive electrode is right as one of battery core part
Battery combination property plays key effect.Existing anode material for lithium-ion batteries mainly have cobalt acid lithium, lithium nickelate, LiMn2O4,
Ternary material and LiFePO4.Wherein lithium iron phosphate positive material has abundant raw materials, cheap, pollution-free, security is good, fill
The advantages of discharge platform is substantially and capacity is moderate, is highly suitable as the positive electrode of lithium ion battery.But due to LiFePO4
Conductance is relatively low, have impact on chemical property.LiFePO4 electric conductivity can be effectively improved using carbon source coated LiFePO 4 for lithium ion batteries, from
And improve its chemical property.The carbon source used at present has glucose, sucrose, polyvinyl alcohol, polyethylene glycol, graphite dilute etc..
Such as Chinese patent CN201310091097.7 discloses a kind of carbon-coated LiFePO 4 for lithium ion batteries lithium ion cell positive and answered
The preparation method of condensation material, comprises the following steps:(1) mix:First source of iron, phosphorus source, lithium source are mixed with carbon source, with ethanol or water
For ball-milling medium, ball milling mixing is carried out, wet mixed material is obtained, the material is vacuum dried, obtains dry mixed material;
(2)Fill kettle, calcining:By step(1)In obtained by dried material be fitted into the closed stainless steel cauldron of high temperature resistant, high pressure,
Heating calcining, calcining heat is 400~650 DEG C, and calcination time is 4~8h, is cooled to room temperature after the completion of calcining, obtains carbon coating
Iron phosphate lithium positive pole composite.
And for example Chinese patent CN201210039290.1 discloses a kind of preparation method of graphene-coated lithium iron phosphate, bag
Include following steps:(1) graphene or graphene oxide are scattered in the aqueous solution, its full and uniform dispersion is made by ultrasound;(2)
In the suspension that step (1) is obtained is dissolved at room temperature as the source of iron of ferric lithium phosphate precursor and inorganic phosphor-contained thing, in inertia
The lithium source as ferric lithium phosphate precursor is added under gas shield and is flowed back;(3) wash and be dried to obtain graphene oxide
Or the LiFePO 4 material of graphene coated;(4) in the final acquisition of Ar mixed gas atmosphere high temperature annealing containing 5v/v%H2
The LiFePO 4 material of graphene coated.
But, because the lithium iron phosphate particles after being coated through above-mentioned carbon source are easily bonded, and hold in follow-up pulverization process
The breakage that comes off of clad is easily caused, the chemical property of material is have impact on.In addition, the phosphorus content of above-mentioned carbon source is typically relatively low,
Would generally occur the decomposable process of a series of complex in heating roasting process, wherein the overwhelming majority is discharged in waste gas form, and
A certain amount of solid fine particle can be taken out of, atmosphere pollution is caused.
The content of the invention
It is an object of the invention to the defect existed for prior art there is provided one kind with isotropism high softening point bitumen
The method that modified phosphate iron lithium anode material is prepared for carbon source, using with high carbon content, isotropic high softening point bitumen
As carbon source coated LiFePO 4 for lithium ion batteries, the lithium iron phosphate particles after cladding are not bonded, it is not necessary to crushed, so as to avoid causing carbon
The breakage of clad, gained modified phosphate iron lithium anode material has the excellent of high discharge capacity, coulombic efficiency and long circulation life
Point, while simplifying the preparation process of material.
The present invention also aims to provide the modified phosphate iron lithium anode material of methods described preparation
The preparation method of the modified phosphate iron lithium anode material of the present invention, comprises the following steps:
(1)Lithium source, source of iron and carbon source mixture are crushed into obtain ferric lithium phosphate precursor;
(2)By step(1)Obtained ferric lithium phosphate precursor is placed in the blast furnace of inert gas 500 DEG C~800 DEG C sintering 8 that heat up
~16 hours, cooling obtained changing surname lithium iron phosphate positive material.
Step(1)Described in lithium source be one or both of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate;Source of iron is
Ferric phosphate;Carbon source is isotropism high softening point bitumen, and carbon content >=85%, softening point is 200~240 °C, toluene insolubles
(TI):70~80 %, quinoline insolubles (QI) 25~35%.
Source of iron is 1 with lithium source mol ratio:1~1.1;Described carbon source accounts for 8%~14% weight of raw material total amount.
The pitch is preferably powdery;The particle diameter of asphalt powder is preferably 1~3 μm.
For the mixture powder uniformly dried, step(1)In, by lithium source, source of iron and carbon source mixture wet ball grinding,
Spray drying.
The dispersion liquid that wet ball grinding is used is water, ethanol, acetone or tetrahydrofuran;The Ball-milling Time preferably 2~6 hours.
Step(2)In, described inert atmosphere is hydrogen, nitrogen or argon gas.
The isotropism high softening point bitumen can use commercially available prod, prepared by the present invention preferably following methods:
(1)Mid temperature pitch raw material is heated to 300-350 °C of temperature, Air blowing 8~10 hours;
(2)Cooling step(1)Obtained pitch, is crushed to 1~3 μm.
Step(2)In, it is preferred to use impact grinder, air-flow vortex formula pulverizer, ultra micro ball mill, pendulum-type
Flour mill crushes the pitch after cooling.
The present invention has the following advantages that compared with prior art:(1)Because the carbon source that the present invention is used is high for isotropism
It will not be bonded together after softening point asphalt, its lithium iron phosphate particles coated sintering, it is not necessary to crushed, it is to avoid cause carbon
The breakage of clad, obtained modified phosphate iron lithium has high discharge capacity, coulombic efficiency and long circulation life, simplifies simultaneously
The preparation technology of material;(2)In the production process of existing lithium iron phosphate positive material, because using sucrose(Carbon content rate 42.10%)、
Glucose(Carbon content rate 36.24%)Deng the low carbon source of carbon content rate, wherein the overwhelming majority is discharged in waste gas form, and it can take out of certain
The solid fine particle of amount, causes atmosphere pollution.The high softening point bitumen that the present invention is more than 85% using carbon content rate is used as carbon source, lithium
One or both of the preferred lithium carbonate in source, lithium hydroxide, lithium acetate, lithium nitrate;Source of iron preferably phosphoric acid iron, passes through optimization of C/C composites
Usage ratio, significantly reduces the discharge amount of exhaust gas in Material Manufacturing Process, more environmentally-friendly.Carbon can be reduced after baking simultaneously
Source volatile component is bonded in equipment, is reduced the maintenance cost to equipment, is improved production efficiency.
Embodiment
Embodiment 1
Mid temperature pitch raw material is heated to 300 °C of temperature, Air blowing 10 hours;Impact grinder is used after cooling
It is crushed to 2 μm.Isotropism high softening point bitumen is obtained, its carbon content is 90%, softening point is 200 °C, toluene insolubles
(TI):80%, quinoline insolubles (QI) 25%.
Amount compares 0.63 by mol:0.37:1, which weighs lithium carbonate, lithium hydroxide and ferric phosphate, obtains compound, then mixed
Close material and add above-mentioned isotropic high softening point bitumen, high softening point bitumen accounts for 10% weight of the total addition of raw material.Will be upper
Stating compound addition, ball milling is after 3 hours in planetary ball mill by dispersant of ethanol, and LiFePO4 forerunner is made in spray drying
Body.Ferric lithium phosphate precursor is placed in high temperature furnace, 800 DEG C of heating high temperature sintering 8 hours under nitrogen atmosphere, cooling obtains phosphoric acid
Iron lithium anode material.
Embodiment 2
Mid temperature pitch raw material is heated to 350 °C of temperature, Air blowing 8 hours;Impact grinder is used after cooling
It is crushed to 3 μm.Isotropism high softening point bitumen is obtained, its carbon content is 85%, softening point is 240 °C, toluene insolubles
(TI):70%, quinoline insolubles (QI) 35%.
Amount compares 1.1 by mol:1 weighs lithium acetate and ferric phosphate obtains compound, is then added in compound above-mentioned each
To the high softening point bitumen of the same sex, the weight of high softening point bitumen accounts for the 14% of the total addition of raw material.By above-mentioned compound add with
Acetone is that ball milling is after 6 hours in planetary ball mill for dispersant, and ferric lithium phosphate precursor is made in spray drying.Before LiFePO4
Drive body to be placed in high temperature furnace, 600 DEG C of heating high temperature sintering 12 hours under hydrogen atmosphere, cooling obtains lithium iron phosphate positive material.
Embodiment 3
Mid temperature pitch raw material is heated to 335 °C of temperature, Air blowing 9 hours;Impact grinder is used after cooling
It is crushed to 1 μm.Isotropism high softening point bitumen is obtained, its carbon content is 95%, softening point is 220 °C, toluene insolubles
(TI):75%, quinoline insolubles (QI)30%.
Amount compares 1 by mol:1 weighs lithium nitrate and ferric phosphate obtains compound, then compound add it is above-mentioned it is each to
The high softening point bitumen of the same sex, the weight of high softening point bitumen accounts for the 8% of the total addition of raw material.Above-mentioned compound is added with four
Hydrogen furans is that ball milling is after 4 hours in planetary ball mill for dispersant, and ferric lithium phosphate precursor is made in spray drying.By LiFePO4
Presoma is placed in high temperature furnace, and 500 DEG C of heating high temperature sintering 16 hours under nitrogen argon gas atmosphere, cooling obtains iron phosphate lithium positive pole material
Material.
Comparative example 1:
Amount compares 0.63 by mol:0.37:1, which weighs lithium chloride, lithium hydroxide and ferric phosphate, obtains compound, then in compound
Sucrose is added, the weight of sucrose accounts for the 10% of the total addition of raw material.Above-mentioned compound is added into celestial body of being expert at by dispersant of ethanol
Ball milling is after 3 hours in grinding machine, and ferric lithium phosphate precursor is made in spray drying.Ferric lithium phosphate precursor is placed in high temperature furnace, nitrogen
800 DEG C of heating high temperature sintering 8 hours under gas atmosphere, cooling, crushing, classification obtain lithium iron phosphate positive material.
Comparative example 2:
Amount compares 0.63 by mol:0.37:1, which weighs lithium chloride, lithium hydroxide and ferric phosphate, obtains compound, then in compound
Add mid temperature pitch(75 °C of fusing point), the weight of mid temperature pitch accounts for the 10% of the total addition of raw material.Above-mentioned compound is added with second
Alcohol is that ball milling is after 3 hours in planetary ball mill for dispersant, and ferric lithium phosphate precursor is made in spray drying.By LiFePO4 forerunner
Body is placed in high temperature furnace, and 600 DEG C of heating high temperature sintering 12 hours under hydrogen atmosphere, cooling, crushing, classification are obtaining LiFePO4 just
Pole material.
Comparative example 3:
Amount compares 0.63 by mol:0.37:1, which weighs lithium chloride, lithium hydroxide and ferric phosphate, obtains compound, then in compound
Add anisotropic high softening point bitumen(268 °C of fusing point), the weight of high softening point bitumen accounts for the 10% of the total addition of raw material.
Above-mentioned compound is added by dispersant of ethanol in planetary ball mill after ball milling 3 hours, the obtained LiFePO4 of spray drying
Presoma.Ferric lithium phosphate precursor is placed in high temperature furnace, 500 DEG C of heating high temperature sintering 16 hours under argon gas atmosphere, cooling, powder
Broken, classification obtains lithium iron phosphate positive material.
Electrochemical property test:
By the positive electrode powder of above-mentioned preparation and 5wt% polyvinylidene fluoride(PVDF) in organic solvent 1-METHYLPYRROLIDONE
(NMP)In uniformly mix, it is then that it is uniform coated in copper foil surface, and in drying 5 hours, afterwards, above-mentioned electrode at 60 DEG C
Further it is compacted, and is dried in vacuo 10 hours in 120 DEG C.By above-mentioned electrode, liquid electrolyte(1M LiPF6 are dissolved in volume
Than for 1:In 1 carbonic acid acetic acid esters and dimethyl carbonate mixed solution), capillary polypropylene barrier film and negative pole composition CR2032 knobs
Battery is detained, constant current charge-discharge experiment is carried out with 0.5mA/cm2 (0.2C) current density, its chemical property is measured.Test knot
Fruit is listed in table 1.
The electrochemical property test result of table 1
It was found from test result, the modified phosphate iron lithium anode material prepared using the present invention, with excellent synthesis electrochemistry
Performance, its first discharging efficiency be up to 99%;Circulation volume conservation rate is more than 98% within 100 weeks.
The carbon source that comparative example 1-3 is used is sucrose, mid temperature pitch, anisotropic high softening point bitumen, lithium source selection
LiCl, LiOH.H2O, the lithium iron phosphate positive material of preparation, its chemical property is substantially not as prepared by inventive formulation and method
Material, show as that irreversible capacity loss first is larger, cycle performance is poor.
Claims (8)
1. a kind of preparation method of modified phosphate iron lithium anode material, it is characterised in that comprise the following steps:
(1)Lithium source, source of iron and carbon source mixture are crushed into obtain ferric lithium phosphate precursor;
(2)By step(1)Obtained ferric lithium phosphate precursor is placed in the blast furnace of inert gas 500 DEG C~800 DEG C sintering 8 that heat up
~16 hours, cooling obtained changing surname lithium iron phosphate positive material;
Step(1)Described in lithium source be one or both of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate;Source of iron is phosphoric acid
Iron;Carbon source is isotropism high softening point bitumen, and carbon content >=85%, softening point is 200~240 °C, toluene insolubles (TI):
70~80 %, quinoline insolubles (QI) 25~35%;
Source of iron is 1 with lithium source mol ratio:1~1.1;Described carbon source accounts for 8%~14% weight of raw material total amount.
2. according to the method described in claim 1, it is characterised in that step(1)In, by lithium source, source of iron and carbon source mixture wet method
Ball milling, spray drying.
3. method according to claim 1 or 2, it is characterised in that the dispersion liquid that the wet ball grinding is used for water, ethanol,
Acetone or tetrahydrofuran;The Ball-milling Time is 2~6 hours.
4. method according to claim 3, it is characterised in that step(2)In, described inert atmosphere is hydrogen, nitrogen or
Argon gas.
5. method according to claim 4, it is characterised in that the pitch is preferably powdery;The particle diameter of asphalt powder is 1~3
μm。
6. method according to claim 5, it is characterised in that the isotropism high softening point bitumen is by following methods system
It is standby to obtain:(1)Mid temperature pitch raw material is heated to 300-350 °C of temperature, Air blowing 8~10 hours;(2)Cooling
Step(1)Obtained pitch, is crushed.
7. method according to claim 6, it is characterised in that step(2)In, using impact grinder,
Air-flow vortex formula pulverizer, ultra micro ball mill or pendulum type ring roll pulverizer crush the pitch after cooling.
8. modified phosphate iron lithium anode material prepared by one of claim 1-7 methods described.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710382828.1A CN106981645A (en) | 2017-05-26 | 2017-05-26 | Modified phosphate iron lithium anode material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710382828.1A CN106981645A (en) | 2017-05-26 | 2017-05-26 | Modified phosphate iron lithium anode material and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106981645A true CN106981645A (en) | 2017-07-25 |
Family
ID=59344196
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710382828.1A Pending CN106981645A (en) | 2017-05-26 | 2017-05-26 | Modified phosphate iron lithium anode material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106981645A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109713303A (en) * | 2018-12-29 | 2019-05-03 | 蜂巢能源科技有限公司 | Prepare method, negative electrode material and the power battery of negative electrode material |
CN110600701A (en) * | 2019-09-18 | 2019-12-20 | 湖南大学 | Lithium ion battery LiMnPO4Preparation method of positive electrode carbon coating |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101693532A (en) * | 2009-10-16 | 2010-04-14 | 清华大学 | Method for preparing lithium ferrous phosphate |
CN103897714A (en) * | 2014-01-09 | 2014-07-02 | 湛江市聚鑫新能源有限公司 | Method for preparing high-softening point asphalt for coating natural graphite cathode material of lithium-ion battery |
CN106058304A (en) * | 2016-08-10 | 2016-10-26 | 广东东岛新能源股份有限公司 | Artificial graphite negative electrode material used for lithium ion power batteries, and preparation method thereof |
-
2017
- 2017-05-26 CN CN201710382828.1A patent/CN106981645A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101693532A (en) * | 2009-10-16 | 2010-04-14 | 清华大学 | Method for preparing lithium ferrous phosphate |
CN103897714A (en) * | 2014-01-09 | 2014-07-02 | 湛江市聚鑫新能源有限公司 | Method for preparing high-softening point asphalt for coating natural graphite cathode material of lithium-ion battery |
CN106058304A (en) * | 2016-08-10 | 2016-10-26 | 广东东岛新能源股份有限公司 | Artificial graphite negative electrode material used for lithium ion power batteries, and preparation method thereof |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109713303A (en) * | 2018-12-29 | 2019-05-03 | 蜂巢能源科技有限公司 | Prepare method, negative electrode material and the power battery of negative electrode material |
CN110600701A (en) * | 2019-09-18 | 2019-12-20 | 湖南大学 | Lithium ion battery LiMnPO4Preparation method of positive electrode carbon coating |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6445585B2 (en) | Porous carbon nanotube microspheres and production method and use thereof, metallic lithium-skeleton carbon composite material and production method thereof, negative electrode, and battery | |
CN101320809B (en) | Lithium ion battery anode material manganese lithium phosphate and preparation method thereof | |
CN107275606B (en) | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof | |
CN103708437B (en) | Soft carbon negative material of lithium ion battery, preparation method of soft carbon negative material and lithium ion battery | |
CN101800311B (en) | Method for preparing lithium iron phosphate with high rate discharge by using ultrasonic coprecipitation | |
CN103985867B (en) | A kind of method preparing carbon cladding ferrosilite lithium composite material | |
WO2011009231A1 (en) | Method for preparing carbon-coated positive material of lithium ion battery | |
CN108682787B (en) | Lithium ion battery pole piece and preparation method thereof | |
CN103137976B (en) | Nano composite material and preparation method thereof and positive electrode and battery | |
CN102856553A (en) | Preparation method of hydrothermal synthesis carbon coated lithium iron phosphate | |
CN108682833B (en) | Preparation method of lithium iron phosphate-based modified cathode material | |
CN105047921A (en) | Lithium ion battery cathode material composite lithium iron phosphate and preparation method thereof and lithium ion battery | |
CN104600296A (en) | Preparation method of Se-C positive electrode composite material of lithium-selenium battery | |
CN104979541A (en) | Lithium titanate composite material and preparation method thereof | |
CN102306791A (en) | Preparation method of carbon-coated non-stoichiometric lithium iron phosphorus oxide material | |
CN104009234B (en) | The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium | |
CN103413918B (en) | A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium | |
CN102903918B (en) | Preparation method for manganese phosphate lithium nanosheet | |
CN106099066A (en) | A kind of germanium dioxide/graphene composite material and preparation method thereof | |
CN102034980B (en) | Lithium iron phosphate-aluminum-carbon composite cathode material and preparation method thereof | |
CN102208624A (en) | Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method | |
CN105742592A (en) | W/W2Preparation method of C/Action Carbon coated lithium ion battery anode material | |
CN104934585B (en) | A kind of vanadium based compound Zn3V3O8And its preparation method and application | |
CN102157727A (en) | Preparation method for nano MnO of negative electrode material of lithium ion battery | |
CN106450186A (en) | Preparation method for lithium manganese silicate/carbon composite material used as positive electrode material of lithium ion battery, and positive electrode slurry and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170725 |
|
RJ01 | Rejection of invention patent application after publication |