CN105932244A - Method for preparing iron-fluorine composite doped lithium manganate positive electrode material by combination of hydrothermal method and two-step sintering method - Google Patents
Method for preparing iron-fluorine composite doped lithium manganate positive electrode material by combination of hydrothermal method and two-step sintering method Download PDFInfo
- Publication number
- CN105932244A CN105932244A CN201610338146.6A CN201610338146A CN105932244A CN 105932244 A CN105932244 A CN 105932244A CN 201610338146 A CN201610338146 A CN 201610338146A CN 105932244 A CN105932244 A CN 105932244A
- Authority
- CN
- China
- Prior art keywords
- source
- lithium
- fluorine
- mol
- 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.)
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
Abstract
The invention discloses a method for preparing an iron-fluorine composite doped lithium manganate positive electrode material by combination of a hydrothermal method and a two-step sintering method. The method comprises the following steps of: (1) dissolving a manganese source and a strong oxidant into distilled water, and reacting in a polytetrafluoroethylene liner in a reaction kettle at 80-180 DEG C for 6-20 hours to obtain MnO2 powder; (2) grinding MnO2, a lithium source, a fluorine ion doping source and an iron source to obtain a mixture; and (3) sintering the mixture in the muffle furnace at 200-600 DEG C for 2-8 hours, grinding the mixture and sintering the product at 650-850 DEG C for 10-30 hours to obtain LiFe<x>Mn<2-x>O<4-2x>F<2x>, wherein x is 0.01-0.2. The technology is simple; the cost is low; the iron-fluorine composite doped lithium manganate positive electrode material which is well crystallized, and small in particles, smooth in surface and regular and uniform in morphology is prepared; and the electrochemical properties, including the first charge and discharge specific capacity, the rate capability and the cycle performance are greatly improved.
Description
Technical field
The present invention relates to a kind of hydro-thermal combine two-step sintering and prepare ferrum and the side of the composite mixed manganate cathode material for lithium of fluorine
Method.
Background technology
Lithium ion battery has that energy density is higher, battery life length, cell voltage high, self-discharge rate effect low, memoryless
, should pollute the advantages such as few, therefore, lithium ion battery is considered most to be hopeful to be applied to electronic vapour by most of researchers
The electrokinetic cell of the vehicles such as car, electric ship, hybrid electric vehicle.In anode material for lithium-ion batteries, chemical property is preferable
Material includes LiNiO2、、LiCoO2, spinel-type LiMn2O4And LiFePO4Deng, wherein spinel lithium manganate has cost of material
Cheap, security performance good, environmental protection, discharge voltage advantages of higher, but LiMn2O4Cycle performance poor, owing to manganese is molten at electrolyte
The change of crystalline phase in dissolving, Jahn-Teller effect and charge and discharge process in liquid, its capacity can occur quickly to decay.
Currently for the capacity deep fades of spinel lithium manganate, research is concentrated mainly on three aspects: adulterates, improve electricity
Solve liquid system and Surface coating.Doping refers to introduce valence state and close with the Mn respectively metal ion of radius and close with O
Anion, typical metal ion such as Al3+、Ni3+、Ti4+、Cu2+、Mg2+、Fe3+、Co3+、Zn2+Deng, anion has F-、Br-、
Cl-.Fe after Fe introducing3+Replace Mn3+, reduce the probability undergone phase transition in charge and discharge process, make Jahn-Teller effect obtain
To suppression, spinel structure becomes more stable, and the cycle performance of positive electrode is improved, but due to Fe3+Instead of part
Mn3+, the Mn that causes3+Reducing, the first charge-discharge capacity of material can decrease.After mixing F, owing to F electronegativity value is
The electronegativity value of 3.98, O is 3.44, F-Electronegativity is more than O2-, electron-withdrawing power is strong, the therefore adhesion O to be compared between F and Mn
Big with Mn, it is suppressed that the dissolving of manganese, improve the stable charge/discharge of material, but F-Doping bigger time, due to Mn3+Increasing
Adding, the first charge-discharge capacity of material can have certain increase therewith, and Jahn-Teller distortion is more serious, and the circulation of material is steady
Qualitative can reduce.
The present invention uses water heat transfer nanometer spherical MnO2, and use the mode of two-step sintering to synthesize manganese as template
Acid lithium anode material, and composite mixed by ferrum, fluorine, to being studied of chemical property improving LiMn2O4.
Summary of the invention
On the basis of it is an object of the invention to suppress Jahn-Teller effect, stablizing the spinel structure of LiMn2O4, thus
Prepare capacity and be not susceptible to the manganate cathode material for lithium that decay, the excellent ferrum of high rate performance and fluorine are composite mixed.
Concretely comprise the following steps:
(1) stoichiometrically weigh 0.01 ~ 0.1 mol strong oxidizer and 0.01 ~ 0.1 mol manganese source, both are placed in beaker
In, it is subsequently adding the deionized water of 50 ~ 180 mL, at ambient temperature will by DF-101S type heat collecting type constant temperature blender with magnetic force
Strong oxidizer and manganese source are thoroughly mixed, and are then transferred to by mixed liquor in the polytetrafluoroethyllining lining of 50 ~ 200 mL, then will
Polytetrafluoroethyllining lining is sealed in stainless steel cauldron, under the conditions of the temperature set is as 80 ~ 180 DEG C, is incubated 6 ~ 20 hours,
Naturally cool to room temperature, filter, be dried 18 ~ 30 hours under the conditions of 60 ~ 100 DEG C, obtain manganese source presoma black powder.
(2) manganese source presoma, 0.005-0.1 mol lithium obtained by 0.005 ~ 0.1 mol step (1) are weighed according to mol ratio
Source, 0.0001 ~ 0.1 fluorine-ion-doped source of mol and 0.0001 ~ 0.1 mol source of iron, be placed in four in beaker and add 10 ~ 30
ML dehydrated alcohol, ultrasonic vibration is put into after 20 ~ 40 minutes in baking oven and is dried under conditions of 50 ~ 120 DEG C, then grinds in mortar
Grind 10 ~ 40 minutes.
(3), after being ground by step (2) gains, 200 ~ 600 DEG C of presintering 2-8 hour it are placed in Muffle furnace, after presintering
Be ground and in Muffle furnace 650 ~ 850 DEG C calcine 10 ~ 30 hours, cool to room temperature with the furnace, obtain ferrum and fluorine is composite mixed
Manganate cathode material for lithium LiMn2-xFexO4-2xF2x, wherein: x=0.01 ~ 0.2.
Described strong oxidizer is one or more of hydrogen peroxide, potassium permanganate, Ammonium persulfate. and sodium peroxydisulfate；
Described manganese source is one or more in manganese acetate, manganese carbonate and Manganous sulfate monohydrate；
Described lithium source is one or more in lithium acetate, lithium carbonate and a hydronium(ion) lithium oxide；
Described iron ion doping source is one or both in iron sesquioxide and hydrated ferric oxide.；
Described fluorine-ion-doped source is ammonium fluoride or lithium fluoride.
The present invention relates to a kind of hydro-thermal and combine two-step sintering and ferrum, the system of fluorine composite mixed raising LiMn2O4 chemical property
Preparation Method, utilizes the simple hydro-thermal method of operation to prepare nanometer thorn spherical manganese dioxide, adds lithium source doping iron, fluorine element,
The temperature and time sintered by control again, prepares better crystallinity degree, granule is tiny, the regular homogeneous ferrum of pattern, fluorion are multiple
Close the positive electrode of doping.By ferrum, the composite mixed chemical property significantly improving material of fluorion so that it is have higher
Specific discharge capacity and good cycle performance and high rate performance.When voltage range is 3.0 ~ 4.4 V, LiFexMn4-xO2-xFxMaterial
Expect that first discharge specific capacity is up to 133.6 mAh/g under 0.2 C multiplying power；Under 0.5 C multiplying power after 80 circulations, discharge specific volume
Amount conservation rate is 83.06%, has excellent cyclical stability；When 2 C multiplying power, the specific discharge capacity of material can reach 92.8
mAh/g.Compared with single anion or cation doping mode, the present invention can significantly improve material cycle performance and
Specific discharge capacity.This preparation method is with low cost, environmental pollution is few, excellent electrochemical performance, and the positive electrode of synthesis is dynamic
The application prospect of power field of power supplies is the most wide, it is adaptable to produce in large quantity.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 obtain ferrum, fluorine-ion-doped before and after the XRD figure of manganate cathode material for lithium.
Fig. 2 is the MnO that the embodiment of the present invention 1 obtains2The SEM figure of presoma.
Fig. 3 be the embodiment of the present invention 1 obtain ferrum, fluorine-ion-doped before and after manganate cathode material for lithium SEM figure, wherein:
C, d be ferrum, fluorine-ion-doped before, e, f be ferrum, fluorine-ion-doped after.
Fig. 4 be the embodiment of the present invention 1 obtain ferrum, fluorine-ion-doped before and after manganate cathode material for lithium in 0.2 C multiplying power
Under first charge-discharge curve chart.
Fig. 5 be the embodiment of the present invention 1 obtain ferrum, fluorine-ion-doped before and after manganate cathode material for lithium high rate performance figure.
Fig. 6 be the embodiment of the present invention 1 obtain ferrum, fluorine-ion-doped before and after manganate cathode material for lithium under 0.5 C multiplying power
Cycle performance figure.
Fig. 7 be the embodiment of the present invention 1 obtain ferrum, fluorine-ion-doped before and after manganate cathode material for lithium AC impedance figure.
Fig. 8 be the embodiment of the present invention 1 obtain ferrum, fluorine-ion-doped before and after manganate cathode material for lithium be 0.1 sweeping speed
Cyclic voltammogram during mv/s.
In figure: the manganate cathode material for lithium that undoped p obtains is labeled as LMO；Ferrum, fluorine-ion-doped lithium manganate cathode material
Material is labeled as LMO-FeF.
Detailed description of the invention
Embodiment 1:
(1) 0.025 mol Ammonium persulfate. and 0.025 mol manganese carbonate are placed in beaker, are subsequently adding the deionization of 80 mL
Water, is thoroughly mixed Ammonium persulfate. and manganese carbonate at ambient temperature by DF-101S type heat collecting type constant temperature blender with magnetic force,
Then mixed liquor is transferred in the polytetrafluoroethyllining lining of 100 mL, then polytetrafluoroethyllining lining is sealed to stainless steel reaction
In still, under the conditions of the temperature set is as 130 DEG C, it is incubated 15 hours, naturally cools to room temperature, filter, dry under the conditions of 90 DEG C
Dry 18 hours, obtain black MnO2Powder.
(2) LiFe is pressed0.06Mn1.94O3.88F0.12Stoichiometric proportion, weigh 0.0194 mol step (1) gained MnO2Powder
End, 0.0093 mol lithium acetate, 0.0012 mol lithium fluoride and 0.0006 mol iron sesquioxide, be placed in four in beaker also
Adding 20 mL dehydrated alcohol, ultrasonic vibration is put into after 30 minutes in baking oven and is dried under conditions of 80 DEG C, then grinds in mortar
Grind 20 minutes.
(3), after step (2) gains being ground, it is placed in Muffle furnace 500 DEG C of presintering 5 hours, grinds after presintering
Mill and in Muffle furnace 750 DEG C calcine 20 hours, cool to room temperature with the furnace, after hand-ground, obtain ferrum and the composite mixed manganese of fluorine
Acid lithium anode material LiFe0.06Mn1.94O3.88F0.12。
Manganate cathode material for lithium LiFe composite mixed to institute's ferrum and fluorine0.06Mn1.94O3.88F0.12It is fabricated to circular pole piece,
It is assembled into button cell.
Concrete operations are as follows: weigh ferrum and the composite mixed manganate cathode material for lithium of fluorine according to mass ratio: acetylene black: PVDF
=8: 1: 1 ratio, is sufficiently stirred for milling, and adds appropriate NMP, furnishing electrode slip, is being coated with equably by slip with spreader
Cloth is on aluminium foil, after 110 DEG C of vacuum drying ovens 15 hours, is washed into the circular pole piece of diameter 15 mm, each pole piece
Quality is at about 1.8 mg.With metal lithium sheet as negative pole, Celgard2300 microporous polypropylene membrane is barrier film, and electrolyte used is l
The LiPF of mol/L6/ EC+DMC+EMC (volume ratio is l:l:l), at relative humidity less than 5%, oxygen forces down in 10 pp, the wettest
Degree is assembled into CR2016 type button cell in certain sequence less than 5% and in the glove box of full argon, then stands 12 hours
After, ac impedance measurement, cyclic voltammetry and charge-discharge test can be carried out.Charging/discharging voltage scope is 3.0 ~ 4.4 V, fills
Discharge-rate is 0.5 C, and its first discharge specific capacity reaches 121.6 mAh/g.After circulating 80 times, discharge capacity is 101 mAh/
G, capability retention is 83.06%.
Embodiment 2:
(1) 0.025 mol Ammonium persulfate. and 0.025 mol manganese carbonate are placed in beaker, are subsequently adding the deionization of 80 mL
Water, is thoroughly mixed Ammonium persulfate. and manganese carbonate at ambient temperature by DF-101S type heat collecting type constant temperature blender with magnetic force,
Then mixed liquor is transferred in the polytetrafluoroethyllining lining of 100 mL, then polytetrafluoroethyllining lining is sealed to stainless steel reaction
In still, under the conditions of the temperature set is as 130 DEG C, it is incubated 15 hours, naturally cools to room temperature, filter, dry under the conditions of 90 DEG C
Dry 18 hours, obtain black MnO2Powder.
(2) LiFe is pressed0.06Mn1.94O3.88F0.12Stoichiometric proportion, weigh 0.0197 mol step (1) gained MnO2Powder
End, 0.0099 mol lithium carbonate, 0.0006 mol lithium fluoride and 0.0003 mol hydrated ferric oxide., be placed in four in beaker and add
Entering 20 mL dehydrated alcohol, ultrasonic vibration is put into after 30 minutes in baking oven and is dried under conditions of 100 DEG C, then grinds in mortar
Grind 20 minutes.
(3), after step (2) gains being ground, it is placed in Muffle furnace 500 DEG C of presintering 5 hours, grinds after presintering
Mill and in Muffle furnace 750 DEG C calcine 20 hours, cool to room temperature with the furnace, after hand-ground, obtain ferrum and the composite mixed manganese of fluorine
Acid lithium anode material LiFe0.06Mn1.94O3.88F0.12。
Manganate cathode material for lithium LiFe composite mixed to synthesized ferrum and fluorine0.06Mn1.94O3.88F0.12It is fabricated to circular pole
Sheet, is assembled into button cell.
Concrete operations are as follows: weigh ferrum and the composite mixed manganate cathode material for lithium of fluorine according to mass ratio: acetylene black: PVDF
=8: 1: 1 ratio, is sufficiently stirred for milling, and adds appropriate NMP, furnishing electrode slip, is being coated with equably by slip with spreader
Cloth is on aluminium foil, after 110 DEG C of vacuum drying ovens 15 hours, is washed into the circular pole piece of diameter 15 mm, each pole piece
Quality is at about 1.8 mg.With metal lithium sheet as negative pole, Celgard2300 microporous polypropylene membrane is barrier film, and electrolyte used is l
The LiPF of mol/L6/ EC+DMC+EMC (volume ratio is l:l:l), at relative humidity less than 5%, oxygen forces down in 10 pp, the wettest
Degree is assembled into CR2016 type button cell in certain sequence less than 5% and in the glove box of full argon, then stands 12 hours
After, ac impedance measurement, cyclic voltammetry and charge-discharge test can be carried out.Charging/discharging voltage scope is 3.0 ~ 4.4 V, fills
Discharge-rate is 0.5 C, and its first discharge specific capacity reaches 116.1 mAh/g.After circulating 80 times, specific discharge capacity is 93.9
MAh/g, capability retention is 80.88%.
Wherein, undoped p obtain manganate cathode material for lithium be labeled as LMO；Ferrum that embodiment 1 obtains, fluorine-ion-doped
Manganate cathode material for lithium be labeled as LMO-FeF；PVDF: Kynoar；NMP:N-N-methyl-2-2-pyrrolidone N；EC: ethylene
Alkene ester；DMC: dimethyl carbonate；EMC: Ethyl methyl carbonate.
Claims (1)
1. a hydro-thermal combines two-step sintering and prepares ferrum and the method for the composite mixed manganate cathode material for lithium of fluorine, it is characterised in that
Concretely comprise the following steps:
(1) 0.01 ~ 0.1 mol strong oxidizer and 0.01 ~ 0.1 mol manganese source are placed in beaker, are subsequently adding 50 ~ 180 mL's
Deionized water, is sufficiently stirred for strong oxidizer and manganese source at ambient temperature by DF-101S type heat collecting type constant temperature blender with magnetic force
Mixing, is then transferred to mixed liquor in the polytetrafluoroethyllining lining of 50 ~ 200 mL, then polytetrafluoroethyllining lining is sealed to not
In rust steel reactor, under the conditions of the temperature set is as 80 ~ 180 DEG C, it is incubated 6 ~ 20 hours, naturally cools to room temperature, filter,
It is dried 18 ~ 30 hours under the conditions of 60 ~ 100 DEG C, obtains manganese source presoma black powder；
(2) by manganese source presoma obtained by 0.005 ~ 0.1 mol step (1), 0.005-0.1 mol lithium source, 0.0001 ~ 0.1
The fluorine-ion-doped source of mol and 0.0001 ~ 0.1 mol source of iron, be placed in four in beaker and add 10 ~ 30 mL dehydrated alcohol, super
Acoustic shock is put into after swinging 20 ~ 40 minutes in baking oven and is dried under conditions of 50 ~ 120 DEG C, then grinds 10 ~ 40 minutes in mortar；
(3), after step (2) gains being ground, it is placed in Muffle furnace 200 ~ 600 DEG C of presintering 2-8 hour, carries out after presintering
Grind and in Muffle furnace 650 ~ 850 DEG C calcine 10 ~ 30 hours, cool to room temperature with the furnace, obtain ferrum and the composite mixed manganese of fluorine
Acid lithium anode material LiMn2-xFexO4-2xF2x, wherein: x=0.01 ~ 0.2；
Described strong oxidizer is one or more of hydrogen peroxide, potassium permanganate, Ammonium persulfate. and sodium peroxydisulfate；
Described manganese source is one or more in manganese acetate, manganese carbonate and Manganous sulfate monohydrate；
Described lithium source is one or more in lithium acetate, lithium carbonate and a hydronium(ion) lithium oxide；
Described iron ion doping source is one or both in iron sesquioxide and hydrated ferric oxide.；
Described fluorine-ion-doped source is ammonium fluoride or lithium fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610338146.6A CN105932244A (en) | 2016-05-21 | 2016-05-21 | Method for preparing iron-fluorine composite doped lithium manganate positive electrode material by combination of hydrothermal method and two-step sintering method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610338146.6A CN105932244A (en) | 2016-05-21 | 2016-05-21 | Method for preparing iron-fluorine composite doped lithium manganate positive electrode material by combination of hydrothermal method and two-step sintering method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105932244A true CN105932244A (en) | 2016-09-07 |
Family
ID=56840998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610338146.6A Pending CN105932244A (en) | 2016-05-21 | 2016-05-21 | Method for preparing iron-fluorine composite doped lithium manganate positive electrode material by combination of hydrothermal method and two-step sintering method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105932244A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106229476A (en) * | 2016-08-11 | 2016-12-14 | 湖南杉杉新能源有限公司 | A kind of Anion-cation multiple dope spinel lithium manganate and preparation method thereof |
| CN106450281A (en) * | 2016-11-10 | 2017-02-22 | 桂林理工大学 | Method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping |
| CN106784657A (en) * | 2016-11-29 | 2017-05-31 | 桂林理工大学 | A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material |
| CN108321374A (en) * | 2018-02-05 | 2018-07-24 | 广东工业大学 | A kind of iron and fluorin-doped composite material and preparation method |
| CN108448092A (en) * | 2018-03-20 | 2018-08-24 | 桂林理工大学 | A kind of preparation method with high rate capability and cycle performance LiMn2O4/three-dimensional graphene composite material |
| CN108630922A (en) * | 2018-04-27 | 2018-10-09 | 东北大学秦皇岛分校 | A kind of lithium manganese phosphate/carbon composite anode material, preparation method and lithium ion battery |
| CN110040782A (en) * | 2019-05-06 | 2019-07-23 | 东北大学秦皇岛分校 | A kind of manganese dioxide, and its preparation method and application |
| CN112897584A (en) * | 2021-01-21 | 2021-06-04 | 湘潭大学 | Lithium-rich manganese-based cathode material with divalent cations doped in lithium layer and preparation method thereof |
| CN113851748A (en) * | 2021-06-23 | 2021-12-28 | 宁波行殊新能源科技有限公司 | Method for recycling and regenerating olivine type cathode material waste of lithium ion battery |
| EP4299773A1 (en) * | 2022-06-30 | 2024-01-03 | Fortum Oyj | Method for processing manganese containing material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476117A (en) * | 2002-08-12 | 2004-02-18 | 成都蜀都纳米材料科技发展有限公司 | Lithium manganese oxygen fluorine composite oxide lithium ion secondary battery positive electrode material |
| CN102280617A (en) * | 2011-07-06 | 2011-12-14 | 中国科学院过程工程研究所 | Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof |
| CN104600286A (en) * | 2015-01-29 | 2015-05-06 | 扬州大学 | Preparation method of positive active material hollow spherical lithium manganate of lithium ion battery |
| CN105304894A (en) * | 2015-10-11 | 2016-02-03 | 桂林理工大学 | Method for preparing high-performance lithium manganite positive electrode material by compound doping |
-
2016
- 2016-05-21 CN CN201610338146.6A patent/CN105932244A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476117A (en) * | 2002-08-12 | 2004-02-18 | 成都蜀都纳米材料科技发展有限公司 | Lithium manganese oxygen fluorine composite oxide lithium ion secondary battery positive electrode material |
| CN102280617A (en) * | 2011-07-06 | 2011-12-14 | 中国科学院过程工程研究所 | Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof |
| CN104600286A (en) * | 2015-01-29 | 2015-05-06 | 扬州大学 | Preparation method of positive active material hollow spherical lithium manganate of lithium ion battery |
| CN105304894A (en) * | 2015-10-11 | 2016-02-03 | 桂林理工大学 | Method for preparing high-performance lithium manganite positive electrode material by compound doping |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106229476B (en) * | 2016-08-11 | 2019-01-01 | 湖南杉杉新能源有限公司 | A kind of Anion-cation multiple dope spinel lithium manganate and preparation method thereof |
| CN106229476A (en) * | 2016-08-11 | 2016-12-14 | 湖南杉杉新能源有限公司 | A kind of Anion-cation multiple dope spinel lithium manganate and preparation method thereof |
| CN106450281A (en) * | 2016-11-10 | 2017-02-22 | 桂林理工大学 | Method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping |
| CN106784657A (en) * | 2016-11-29 | 2017-05-31 | 桂林理工大学 | A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material |
| CN108321374A (en) * | 2018-02-05 | 2018-07-24 | 广东工业大学 | A kind of iron and fluorin-doped composite material and preparation method |
| CN108448092A (en) * | 2018-03-20 | 2018-08-24 | 桂林理工大学 | A kind of preparation method with high rate capability and cycle performance LiMn2O4/three-dimensional graphene composite material |
| CN108630922A (en) * | 2018-04-27 | 2018-10-09 | 东北大学秦皇岛分校 | A kind of lithium manganese phosphate/carbon composite anode material, preparation method and lithium ion battery |
| CN108630922B (en) * | 2018-04-27 | 2020-09-01 | 东北大学秦皇岛分校 | Lithium manganese phosphate/carbon composite positive electrode material, preparation method thereof and lithium ion battery |
| CN110040782A (en) * | 2019-05-06 | 2019-07-23 | 东北大学秦皇岛分校 | A kind of manganese dioxide, and its preparation method and application |
| CN110040782B (en) * | 2019-05-06 | 2021-07-27 | 东北大学秦皇岛分校 | Manganese dioxide, preparation method and application thereof |
| CN112897584A (en) * | 2021-01-21 | 2021-06-04 | 湘潭大学 | Lithium-rich manganese-based cathode material with divalent cations doped in lithium layer and preparation method thereof |
| CN113851748A (en) * | 2021-06-23 | 2021-12-28 | 宁波行殊新能源科技有限公司 | Method for recycling and regenerating olivine type cathode material waste of lithium ion battery |
| EP4299773A1 (en) * | 2022-06-30 | 2024-01-03 | Fortum Oyj | Method for processing manganese containing material |
| WO2024003452A1 (en) * | 2022-06-30 | 2024-01-04 | Fortum Oyj | Method for processing manganese containing material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105932244A (en) | Method for preparing iron-fluorine composite doped lithium manganate positive electrode material by combination of hydrothermal method and two-step sintering method | |
| Tang et al. | Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2 | |
| CN102437323B (en) | Anode material of lithium ion battery and preparation method thereof | |
| CN102324511B (en) | Preparation method for lithium ion battery composite cathode material | |
| CN103904321B (en) | The high-temperature solid phase preparation method of lithium ion battery negative material LiMn2O4 | |
| CN105140492A (en) | Cobalt-nickel lithium manganate composite positive electrode material with surface wrapped by lithium zirconate and preparation method | |
| CN106602016A (en) | Preparation method for ammonium fluoride modified nickel-cobalt-aluminum ternary positive electrode material | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| CN107403913A (en) | A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof | |
| CN102403505B (en) | Method for preparing in-situ carbon coated lithium manganese borate composite material by lithium ion battery cathode material | |
| CN102427129A (en) | Lithium ion battery composite negative electrode material, its preparation method, negative electrode with application of material thereof and lithium ion battery | |
| CN103390748B (en) | A kind of preparation method of alumina-coated lithium cobaltate cathode material | |
| CN105185954A (en) | LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof | |
| CN107302083A (en) | A kind of solid reaction process preparation method of nickel lithium manganate cathode material | |
| CN102956883A (en) | AnodePositive electrode material of lithium ion battery with porous laminated structure and preparation method thereof | |
| CN104218233A (en) | Composite lithium ion battery positive electrode material with high rate performance and preparation method of material | |
| CN108091854A (en) | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof | |
| CN105024067A (en) | Lithium ion battery, composite doping modified positive electrode active material thereof and preparation method | |
| CN102201574B (en) | Oxygen-vacancy-containing lithium ferrous silicate and carbon composite anode material and preparation method | |
| Kong et al. | Synthesis of lithium rich layered oxides with controllable structures through a MnO2 template strategy as advanced cathode materials for lithium ion batteries | |
| CN102838102A (en) | Preparation method of lithium iron phosphate monocrystalline nanorods | |
| CN105958027B (en) | A kind of manganese base composite positive pole and preparation method thereof | |
| CN106784657A (en) | A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material | |
| CN106025199A (en) | Preparation method of nanometer lithium lanthanum titanate coated 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2 material | |
| CN104409705A (en) | Preparation method of carbon-coated germanium-doped lithium manganate composite cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160907 |
|
| WD01 | Invention patent application deemed withdrawn after publication |