CN104518217A - Battery grade iron and manganese phosphate and preparation method thereof - Google Patents
Battery grade iron and manganese phosphate and preparation method thereof Download PDFInfo
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- CN104518217A CN104518217A CN201510027348.4A CN201510027348A CN104518217A CN 104518217 A CN104518217 A CN 104518217A CN 201510027348 A CN201510027348 A CN 201510027348A CN 104518217 A CN104518217 A CN 104518217A
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- 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
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- 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
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention relates to battery grade iron and manganese phosphate and a preparation method thereof. The chemical composition of the battery grade iron and manganese phosphate is MnxFe(1-x)PO4, wherein x is greater than or equal to 0.1 and smaller than or equal to 0.9; the preparation method comprises the steps of adopting a hydrothermal oxidation-coprecipitation technology, putting a soluble phosphorus source, iron source and manganese source solution into a reaction kettle according to the chemical composition MnxFe(1-x)PO4 of the iron and manganese phosphate, adding a surfactant and nitric acid, controlling the system pH value to be within 1 to 4, stirring for 2 to 48 h at 100 to 250 DEG C, so as to perform hydrothermal reaction, obtaining turbid liquid containing MnxFe(1-x)PO4.yH2O precipitate, naturally cooling the turbid liquid to room temperature, filtering, washing and drying, obtaining MnxFe(1-x)PO4.yH2O, performing high-temperature roasting at 250 to 700 DEG C, and then obtaining the battery grade iron and manganese phosphate not containing crystal water. The method is simple and practicable, and is easy to realize scale production, the prepared iron and manganese phosphate has the advantages that size distribution is uniform, the purity is high, and iron and manganese elements realize atomic-scale uniform distribution, and the battery grade iron and manganese phosphate a belongs to the optimal precursor for preparing lithium ferric manganese phosphate battery materials.
Description
Technical field
The invention belongs to new energy materials field, particularly prepare battery-grade iron phosphate manganese by the oxidation-coprecipitation technology under hydro thermal method condition, it is the presoma preparing lithium ferric manganese phosphate positive electrode the best.
Background technology
The features such as ferric phosphate lithium cell is safe, pollution-free with its height, long-life have been widely used in the field such as new-energy automobile, scale energy storage.Compared with battery material such as cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate etc., advantages such as the LiFePO4 of olivine structural has safely, have extended cycle life, cheap and being concerned, adopt the new-energy automobile of lithium iron phosphate dynamic battery to propagate its belief on a large scale, the fund subsidy obtaining government is widelyd popularize in each big city.The LiFePO4 energy-storage battery that the stand-by power supply of wind light generation energy storage, communication base station also gradually adopts performance more excellent at present, and do not re-use lead acid accumulator.
But ferric phosphate lithium cell voltage is only 3.2V, and energy density is only 80-120Wh/kg, have a strong impact on the automobile course continuation mileage carrying ferric phosphate lithium cell.New-energy automobile is little due to space, requires high to energy density, and the electricity that the battery of unit volume and Unit Weight is released is more, fills the mileage that electrical travelling sails longer.A lot of electrokinetic cell nickle cobalt lithium manganate of turning to energy density higher or nickel cobalt lithium aluminate battery for this reason, but there is serious safety issue and limit its application in these batteries.The fail safe of LiFePO 4 material has benefited from its stable olivine structural.Researcher develops the phosphate system battery materials such as lithium manganese phosphate, cobalt phosphate lithium, lithium ferric manganese phosphate on the basis of LiFePO4 for this reason.
Lithium ferric manganese phosphate battery material obtains extensive concern and research at present.It has the specific capacity (170mAh/g) identical with LiFePO4, but has higher discharge voltage (3.9 ~ 4.0V, vs.Li), and energy density improves 20% on the basis of LiFePO4.Lithium ferric manganese phosphate is expected to replace LiFePO4 and become new power and the first-selected positive electrode of energy-storage lithium battery.
But the synthetic method of lithium ferric manganese phosphate is all adopt lithium source at present, source of iron, manganese source, phosphorus source mixes, grinding, the technique of roasting, or adopt the method first preparing presoma, as the publication number patent of invention that is CN102969506A discloses the preparation method of a kind of modified phosphate ferrimanganic lithium and presoma thereof, presoma is wherein ferrimanganic mixture, it adopts ferrous oxalate, iron oxide, the source of iron of iron powder ferric phosphate or ferrous phosphate, with manganese dioxide, the manganese source of mangano-manganic oxide or manganese powder, and mix and blend is carried out in phosphorus source, react under 60-100 degree, then drying and crushing pre-burning again, as presoma.But this invention is not added oxidant and do not added reducing agent yet, the material more complicated that reaction is formed, can not form manganic and ferric phosphate.Like this considerable influence is had to the mol ratio of iron, manganese, phosphorus in the final lithium ferric manganese phosphate product generated, do not become stable olivine structural, and then have influence on product electrical property.
Summary of the invention
The present invention is directed to above-mentioned deficiency, propose a kind of battery-grade iron phosphate manganese and preparation method thereof, described battery-grade iron phosphate manganese consists of Mn
xfe
(1-x)pO
4, wherein=0.01≤x≤0.99, the valent state of Mn and Fe is positive trivalent.
The present invention adopts the oxidation-coprecipitation technology under hydro thermal method condition, adopts following technical scheme, comprises step as follows:
By the chemical composition Mn of battery-grade iron phosphate manganese
xfe
(1-x)pO
4take required soluble sources, source of iron, manganese source compound, wherein mol ratio (Fe+Mn): P=1:1, respectively phosphorus source, source of iron, manganese source compound are dissolved and form solution in deionized water, and be placed in reactor mixing and stirring, add surfactant, nitric acid, hierarchy of control pH value is 1 ~ 4, stir with the speed of 100 ~ 500r/min at 100 ~ 250 DEG C and carry out reaction 2 ~ 48h, obtain containing Mn
xfe
(1-x)pO
4yH
2the suspension-turbid liquid of O precipitation, naturally cools to room temperature; Suspension-turbid liquid filtration, washing, drying are obtained Mn
xfe
(1-x)pO
4yH
2o, then 250 ~ 700 DEG C of high-temperature roastings, obtain not containing the battery-grade iron phosphate manganese of the crystallization water.
For realizing object of the present invention further, described soluble sources is phosphoric acid, sodium phosphate, sodium dihydrogen phosphate, ammonium phosphate.
For realizing object of the present invention further, described soluble manganese source is the one in manganese nitrate, manganese sulfate, manganese chloride.
For realizing object of the present invention further, described solubility source of iron is the one in ferrous sulfate, ferric nitrate, iron chloride, ferric sulfate.
For realizing object of the present invention further, described surfactant is the one in sodium cetanesulfonate, hexadecylamino acid, cetyl ichthyodin, in order to control precipitation formation speed and refinement product granularity.
For realizing object of the present invention further, the described nitric acid added at 100 ~ 250 DEG C for being oxidized Mn respectively
2+and Fe
2+for Mn
3+and Fe
3+, then with PO
4 3-be combined into Mn
xfe
(1-x)pO
4precipitation.
Battery-grade iron phosphate manganese of the present invention and preparation method thereof, its beneficial effect shows:
1, the present invention is the oxidation-coprecipitation technology under hydrothermal condition.Oxidation refers to: by nitric acid oxidizability at a certain temperature, the manganese of oxidation divalence and iron, and form manganese and the iron of trivalent, the chemical reaction equation of this process is:
Mn
2++NO
3 -+2H
+→Mn
3++NO
2+H
2O
Fe
2++NO
3 -+2H
+→Fe
3++NO
2+H
2O
Co-precipitation refers to: the manganese of trivalent and iron are combined the solid solution forming phosphoric acid ferrimanganic homogeneous phase again and precipitate with phosphate radical, and in compound precipitates, iron and manganese are dispersed, atom level mixing, and the chemical reaction equation of this process is:
(1-x) Fe
3++ Mn
3++PO
4 3-+yH
2O→Mn
xFe
(1-x) PO
4·yH
2O
The existence of surfactant simultaneously, serve the effect controlling precipitation formation speed and refinement product granularity, make product have more tiny particle, pattern is more regular, spherical in shape, even particle size distribution;
Hydro thermal method refers to: under hydrothermal conditions, crystallization is more tight, particle size distribution is more even for the ferric phosphate manganese solid solution precipitation of formation.Three processes are carried out simultaneously, be conducive to iron in product, manganese atom is dispersed, form uniform single compound crystal phase, instead of the mixture of ferric phosphate and manganese phosphate;
2, in the ferric phosphate manganese compound prepared, the mole sum of manganese and iron is equal with phosphate radical, the ratio of the two is 1:1, and the ratio of manganese and iron can adjust arbitrarily according to the needs of synthesis lithium ferric manganese phosphate, ensure that the adjustability of raw material during subsequent production lithium ferric manganese phosphate battery material; Use phosphoric acid ferrimanganic of the present invention directly to mix lithium carbonate or lithium hydroxide, carbon source, carry out high-temperature roasting, under high temperature, ferric iron, manganic generation carbothermic reduction reaction are reduced to ferrous iron and bivalent manganese, can obtain high-performance lithium ferric manganese phosphate (LiMn
xfe
(1-x)pO
4) battery material, decrease raw material type and quantity, be easy to the Homogeneous phase mixing between raw material;
3, the present invention is simple, is easy to accomplish scale production, and the phosphoric acid ferrimanganic of preparation has that even particle size distribution, purity are high, iron and manganese element reach the advantages such as atom level is evenly distributed, and is the best presoma preparing lithium ferric manganese phosphate battery material.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
By the chemical composition Mn of battery-grade iron phosphate manganese
0.1fe
0.9pO
4, take 251gMn (NO
3)
24H
2o, 3634.6gFe (NO
3)
39H
2o, 115.29g SPA (mass fraction is 85%), join and add deionized water in the reactor of 200L and dissolve completely, add 0.5g sodium cetanesulfonate, be uniformly mixed under the speed of 150r/min, use nitric acid, hierarchy of control pH value, at 3-3.5, controls reactor solution temperature to 150 DEG C, continue to stir under the speed of 150r/min to carry out reaction 5h, Mn
2+be oxidized by nitric acid as Mn
3+, Mn
3+and Fe
3+with PO
4 3-in conjunction with generation Mn
0.1fe
0.9pO
4yH
2o precipitates.Obtain containing Mn
0.1fe
0.9pO
4the suspension-turbid liquid of yH2O precipitation, naturally cools to room temperature, is carried out filtering, washing by suspension-turbid liquid filter press, obtains not containing the filter cake of nitrate anion, then roasting at 350 DEG C, removes free water and the crystallization water, obtains LITHIUM BATTERY Mn
0.1fe
0.9pO
4.
Embodiment 2
By the chemical composition Mn of battery-grade iron phosphate manganese
0.7fe
0.3pO
4, take 1.76kgMnCl
24H
2o, 1.667kgFeSO
47H
2o, 2.30kgNH
4h
2pO
4join and add deionized water in the reactor of 200L and dissolve completely, add the acid of 2g hexadecylamino, be uniformly mixed under the speed of 500r/min, nitric acid is used to regulate solution ph at 1-1.2, control reactor solution temperature to 200 DEG C, continue to stir under the speed of 500r/min to carry out reaction 40h, obtain containing Mn
0.7fe
0.3pO
4yH
2the suspension-turbid liquid of O precipitation, naturally cools to room temperature, is carried out filtering, washing by suspension-turbid liquid filter press, obtain not containing the filter cake of the foreign ions such as nitrate anion, sulfate radical, chloride ion, ammonium root, roasting at 500 DEG C again, removes free water and the crystallization water, obtains LITHIUM BATTERY Mn
0.7fe
0.3pO
4.
Embodiment 3
By the chemical composition Mn of battery-grade iron phosphate manganese
0.4fe
0.6pO
4, take 1.014kgMnSO
4h
2o, 3.634kgFe (NO
3)
39H
2o, 1.8kgNaH
2pO
4join and add deionized water in the reactor of 200L and dissolve completely, add 1g cetyl ichthyodin, be uniformly mixed under the speed of 250r/min, nitric acid is used to regulate solution ph at 1.5-2, control reactor solution temperature to 120 DEG C, continue to stir under the speed of 250r/min to carry out reaction 20h, obtain containing Mn
0.4fe
0.6pO
4yH
2the suspension-turbid liquid of O precipitation, naturally cools to room temperature, is carried out filtering, washing by suspension-turbid liquid filter press, obtain the filter cake of ion free from foreign meter, then roasting at 650 DEG C, removes free water and the crystallization water, obtains LITHIUM BATTERY Mn
0.4fe
0.6pO
4.
Above content is only the citing and explanation done the present invention; affiliated those skilled in the art do various amendment to described specific embodiment or supplement; only otherwise depart from design of the present invention or surmount this scope as defined in the claims, protection scope of the present invention all should be belonged to.
Claims (7)
1. a battery-grade iron phosphate manganese, is characterized in that: described battery-grade iron phosphate manganese consists of Mn
xfe
(1-x)pO
4, wherein 0.01≤x≤0.99, the valent state of Mn and Fe is positive trivalent.
2. the preparation method of a kind of battery-grade iron phosphate manganese according to claim 1, it is characterized in that the oxidation-coprecipitation technology under employing hydro thermal method condition, its step is as follows:
By the chemical composition Mn of battery-grade iron phosphate manganese
xfe
(1-x)pO
4take required soluble sources, source of iron, manganese source compound, wherein mol ratio (Fe+Mn): P=1:1, respectively phosphorus source, source of iron, manganese source compound are dissolved and form solution in deionized water, and be placed in reactor mixing and stirring, add surfactant, nitric acid, hierarchy of control pH value is 1 ~ 4, stir with the speed of 100 ~ 500r/min at 100 ~ 250 DEG C and carry out reaction 2 ~ 48h, obtain containing Mn
xfe
(1-x)pO
4yH
2the suspension-turbid liquid of O precipitation, naturally cools to room temperature; Suspension-turbid liquid filtration, washing, drying are obtained Mn
xfe
(1-x)pO
4yH
2o, then 250 ~ 700 DEG C of high-temperature roastings, obtain not containing the battery-grade iron phosphate manganese of the crystallization water.
3. preparation method according to claim 2, is characterized in that described soluble sources is phosphoric acid, sodium phosphate, sodium dihydrogen phosphate, ammonium phosphate.
4. preparation method according to claim 2, is characterized in that described soluble manganese source is the one in manganese nitrate, manganese sulfate, manganese chloride.
5. preparation method according to claim 2, is characterized in that described solubility source of iron is the one in ferrous sulfate, ferric nitrate, iron chloride, ferric sulfate.
6. preparation method according to claim 2, is characterized in that described surfactant is the one in sodium cetanesulfonate, hexadecylamino acid, cetyl ichthyodin, in order to control precipitation formation speed and refinement product granularity.
7. preparation method according to claim 2, is characterized in that, the nitric acid added at 100 ~ 250 DEG C for being oxidized Mn respectively
2+and Fe
2+for Mn
3+and Fe
3+, then with PO
4 3-be combined into Mn
xfe
(1-x)pO
4precipitation.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104934601A (en) * | 2015-06-15 | 2015-09-23 | 北京石油化工学院 | Preparation method of lithium manganese ferric phosphate anode material |
| CN105226245A (en) * | 2015-08-27 | 2016-01-06 | 北大先行科技产业有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN105449207A (en) * | 2015-12-25 | 2016-03-30 | 中钢集团安徽天源科技股份有限公司 | Preparation method of manganese iron phosphate and product |
| CN106252657A (en) * | 2015-06-04 | 2016-12-21 | 深圳市比克电池有限公司 | A kind of anode material of lithium battery preparation method |
| CN106981656A (en) * | 2017-05-13 | 2017-07-25 | 合肥国轩高科动力能源有限公司 | Preparation method of battery-grade ferromanganese phosphate |
| CN107482217A (en) * | 2017-08-08 | 2017-12-15 | 沈丽娜 | A kind of preparation method of modified phosphate ferromanganese lithium |
| CN107697899A (en) * | 2017-10-31 | 2018-02-16 | 中钢集团安徽天源科技股份有限公司 | Preparation method, lithium ferric manganese phosphate, cell positive material and the secondary cell of battery-grade iron phosphate manganese |
| CN109103452A (en) * | 2018-08-28 | 2018-12-28 | 重庆大学 | The preparation method of nano lithium iron manganese anode composite material |
| CN109326777A (en) * | 2018-08-28 | 2019-02-12 | 北京泰丰先行新能源科技有限公司 | A kind of preparation method of lithium iron phosphate cell material |
| CN111908442A (en) * | 2020-08-07 | 2020-11-10 | 上海华谊（集团）公司 | Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof |
| CN113451593A (en) * | 2020-12-10 | 2021-09-28 | 江南大学 | Preparation method and application of amorphous nitrogen-doped ferrocobalt phosphate micro-tablet |
| CN113659134A (en) * | 2021-07-09 | 2021-11-16 | 江苏乐能电池股份有限公司 | Method for preparing nanoscale lithium manganese iron phosphate material by using co-crystallization method |
| CN113871596A (en) * | 2021-09-27 | 2021-12-31 | 湖南亿普腾科技有限公司 | Lithium composite material, preparation method of lithium ion battery cathode material and lithium ion battery |
| CN114940485A (en) * | 2022-07-25 | 2022-08-26 | 蜂巢能源科技股份有限公司 | Lithium iron manganese phosphate precursor and preparation method and application thereof |
| CN115321506A (en) * | 2022-07-28 | 2022-11-11 | 安徽格派新能源有限公司 | Preparation method of high-compaction modified lithium manganese iron phosphate cathode material |
| CN115321507A (en) * | 2022-08-25 | 2022-11-11 | 广东邦普循环科技有限公司 | Method for preparing ferromanganese phosphate by coprecipitation and application thereof |
| WO2023092989A1 (en) * | 2021-11-23 | 2023-06-01 | 湖北融通高科先进材料集团股份有限公司 | Ferrous manganese phosphate, and preparation method therefor and use thereof |
| CN117509596A (en) * | 2023-11-23 | 2024-02-06 | 新洋丰农业科技股份有限公司 | Preparation method of ferric manganese phosphate solid solution and ferric manganese lithium phosphate |
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| CN106252657A (en) * | 2015-06-04 | 2016-12-21 | 深圳市比克电池有限公司 | A kind of anode material of lithium battery preparation method |
| CN104934601A (en) * | 2015-06-15 | 2015-09-23 | 北京石油化工学院 | Preparation method of lithium manganese ferric phosphate anode material |
| CN105226245A (en) * | 2015-08-27 | 2016-01-06 | 北大先行科技产业有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN105226245B (en) * | 2015-08-27 | 2018-03-09 | 青海泰丰先行锂能科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN105449207A (en) * | 2015-12-25 | 2016-03-30 | 中钢集团安徽天源科技股份有限公司 | Preparation method of manganese iron phosphate and product |
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| CN107482217A (en) * | 2017-08-08 | 2017-12-15 | 沈丽娜 | A kind of preparation method of modified phosphate ferromanganese lithium |
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| CN107697899A (en) * | 2017-10-31 | 2018-02-16 | 中钢集团安徽天源科技股份有限公司 | Preparation method, lithium ferric manganese phosphate, cell positive material and the secondary cell of battery-grade iron phosphate manganese |
| CN109103452A (en) * | 2018-08-28 | 2018-12-28 | 重庆大学 | The preparation method of nano lithium iron manganese anode composite material |
| CN109326777A (en) * | 2018-08-28 | 2019-02-12 | 北京泰丰先行新能源科技有限公司 | A kind of preparation method of lithium iron phosphate cell material |
| CN111908442A (en) * | 2020-08-07 | 2020-11-10 | 上海华谊（集团）公司 | Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof |
| CN111908442B (en) * | 2020-08-07 | 2022-12-09 | 上海华谊（集团）公司 | Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof |
| CN113451593A (en) * | 2020-12-10 | 2021-09-28 | 江南大学 | Preparation method and application of amorphous nitrogen-doped ferrocobalt phosphate micro-tablet |
| CN113659134A (en) * | 2021-07-09 | 2021-11-16 | 江苏乐能电池股份有限公司 | Method for preparing nanoscale lithium manganese iron phosphate material by using co-crystallization method |
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| CN115321507B (en) * | 2022-08-25 | 2023-07-07 | 广东邦普循环科技有限公司 | Method for preparing ferric manganese phosphate by coprecipitation and application thereof |
| CN115321507A (en) * | 2022-08-25 | 2022-11-11 | 广东邦普循环科技有限公司 | Method for preparing ferromanganese phosphate by coprecipitation and application thereof |
| WO2024040903A1 (en) * | 2022-08-25 | 2024-02-29 | 广东邦普循环科技有限公司 | Method for preparing ferromanganese phosphate by coprecipitation and use thereof |
| CN117509596A (en) * | 2023-11-23 | 2024-02-06 | 新洋丰农业科技股份有限公司 | Preparation method of ferric manganese phosphate solid solution and ferric manganese lithium phosphate |
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