CN104347875A - Positive electrode material lithium iron manganese phosphate of lithium-ion battery and a preparing method of positive electrode material - Google Patents
Positive electrode material lithium iron manganese phosphate of lithium-ion battery and a preparing method of positive electrode material Download PDFInfo
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- CN104347875A CN104347875A CN201410505399.9A CN201410505399A CN104347875A CN 104347875 A CN104347875 A CN 104347875A CN 201410505399 A CN201410505399 A CN 201410505399A CN 104347875 A CN104347875 A CN 104347875A
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- lithium
- source compound
- ion battery
- manganese
- phosphoric acid
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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
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
Abstract
The invention relates to a method for preparing a positive electrode material lithium iron manganese phosphate of a lithium-ion battery, and belongs to the technical field of new energy materials. According to the technical scheme, the positive electrode material includes the following components and is prepared by the following steps: weighing components of a mixture, namely a lithium source compound, an iron source compound, a manganese source compound, and a phosphorus source compound, and mixing uniformly the components according to the molar ratio of lithium to iron to manganese phosphorus being (1.0-1.2): (0.1-0.9): (0.1-0.9): 1; and preparing a precursor, namely dissolving 2wt%-5 wt% carbon source compound by using an organic solvent in a ball milling tank beforehand, putting the mixture into the ball milling tank and carrying out ball milling for 1-5 hours, the manganese lithium iron phosphate precursor slurry obtained ball milling into a combination oven, and carrying out chemical combination for 2-3 minutes to obtain the precursor. The positive electrode material lithium iron manganese phosphate of the lithium-ion battery, which is prepared by using the method, has a structural formula of LiFexMnyPO4/C and the discharging level being 4.1V and thus has high energy density. In addition, the method disclosed by the invention is simple to operate, has no pollution to the environment, is low in cost, and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery positive pole material phosphoric acid ferrimanganic lithium, belong to energy new material technology field.
Background technology
At present, lithium ion battery is a kind of green high-capacity battery, is widely used in various portable electronic product and communication tool, has a good application prospect in electric automobile.
At polyanion class battery material LiMPO
4in, to have the LiFePO of olivine structural
4for example, it is one of popular anode material for lithium-ion batteries of Recent study, it has high stability, safety and reliability, more environmental protection and the advantage such as cheap, this material is accelerated in industrialization recent years speed, is widely used in lithium-ion-power cell.But the discharge platform of lithium iron phosphate dynamic battery is lower at present, and 3.4V, room-temperature conductivity is poor, can not meet people to electrokinetic cell requirement.The conductivity order of magnitude of lithium manganese phosphate is 10
-14s/cm, than LiFePO4 also low 5 orders of magnitude, mean that maximum possible plays the chemical property of this material, certainly will require the primary particle nanometer more of lithium manganese phosphate, carbon coating layer is more perfect.Based on the characteristic of lithium manganese phosphate and LiFePO 4 material, both common melt body lithium ferric manganese phosphates can be prepared, by the Mn of proper ratio
2+replace iron position atom, significantly the reduction potential of integral material can be brought up to 4.1V, 4.8V, 5.1V from 3.4V.
Wherein, each side combination property of lithium ferric manganese phosphate is the highest, will be embodied in practical application: the conductivity order of magnitude is between LiFePO4 and lithium manganese phosphate; In olivine crystal structure, reduction potential due to iron 600-700mV lower than manganese, can ensure that the capacity of corresponding proportion is in the field of high potential by the substitute proportion of manganese ion, thus significantly improve the energy density of lithium ferric manganese phosphate material, and then improve the energy density of overall battery core; Within the more important thing is that the reduction potential of 4.1V is in the electrochemical window of the electrolyte of current voluminous industry, be convenient to follow-up extensive industrialization and carry out.
Summary of the invention
The object of the present invention is to provide a kind of preparation temperature low, the reaction time is short, and technological operation is simple, and the uniform LiFe of material particle size
xmn
ypO
4anode material for lithium-ion batteries machine preparation method.For this reason, by the following technical solutions, it comprises following component and preparation process in the present invention:
(1) component of mixture
Take Li source compound, Fe source compound, manganese source compound, P source compound, in lithium: iron: manganese: phosphorus mol ratio is that the ratio of 1.0 ~ 1.2:0.1 ~ 0.9:0.1 ~ 0.9:1 mixes.
(2) preparation of presoma
In advance with the carbon-source cpd of organic solvent dissolution 2wt% ~ 5wt% in ball grinder, then mixture is put into ball grinder and carry out ball milling 1 ~ 5h, lithium ferric manganese phosphate precursor pulp after ball milling is put into chemical combination stove and carries out the process of 2-30min chemical combination, obtain presoma.
(3) lithium ferric manganese phosphate is synthesized
Take out presoma grinding, compressing tablet, in inert gas atmosphere, be heated to 600 ~ 900 DEG C, and continue calcining 5 ~ 20h at 600 ~ 900 DEG C, namely obtain the lithium ferric manganese phosphate that target product carbon is coated.
Above-mentioned Li source compound be selected from lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate one or more.
Above-mentioned Fe source compound be selected from ferric phosphate, iron hydroxide, ferric acetate one or more.
Above-mentioned manganese source compound be selected from manganese oxalate, the sub-manganese of acetic acid, manganese dioxide, manganous hydroxide one or more.
Above-mentioned P source compound be selected from ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid one or more.
Above-mentioned carbon-source cpd be selected from sucrose, glucose, soluble starch, citric acid one or more.
Above-mentioned organic solvent be selected from industrial alcohol, absolute ethyl alcohol, acetone, deionized water one or more.
Above-mentioned inert gas is selected from the one in argon gas, helium, nitrogen.
The lithium ion anode material lithium ferric manganese phosphate structural formula prepared by said method is LiFe
xmn
ypO
4/ C, its discharge platform is 4.1V, makes it have high-energy-density, and the present invention is simultaneously simple to operate, and environmentally safe is cheap, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the LiFe that the embodiment of the present invention 1 obtains
xmn
ypO
4the SEM figure of/C;
Fig. 2 is the LiFe that the embodiment of the present invention 1 obtains
xmn
ypO
40.2C charge/discharge capacity-voltage performance the curve chart of/C;
Fig. 3 is the LiFe that the embodiment of the present invention 1 is worth
xmn
ypO
41C discharge capacity-cycle-index the performance chart of/C.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described:
Embodiment 1
0.5-0.6:0.5:0.5:1 weighs a certain amount of lithium carbonate, ferric acetate, the sub-manganese of acetic acid and ammonium dihydrogen phosphate in molar ratio; then add in the ball grinder of prior water-soluble solution 3% glucose; carry out ball milling 40min; after ball milling, slurry is put into chemical combination stove chemical combination 10min, obtain lithium ferric manganese phosphate presoma, then by presoma grinding, compressing tablet; under inert gas atmosphere protection; 700 DEG C of calcining 7h, cool to room temperature with the furnace, obtain the lithium ferric manganese phosphate positive electrode that carbon is coated.
As shown in Figure 1, as can be seen from the figure, sample is loose and porous structure to the surface topography of sample, and most of particle diameter, at 1 μm, has a small amount of agglomeration.
With the lithium ion battery positive pole material phosphoric acid ferrimanganic lithium of preparation for positive electrode, acetylene black is conductive agent, and polytetrafluoroethylene is binding agent, makes electrode slice, take lithium metal as negative pole, is assembled into simulation button cell.Test under 2.3 ~ 4.5V, 0.2C charging and discharging currents condition, the results are shown in accompanying drawing 2.Fig. 3 is this product capacity-cycle performance curve, and 1C circulation 100 weeks rear capability retentions are 95%.
Embodiment 2
1.0 ~ 1.2:0.4:0.6:1 weighs lithium hydroxide, ferric acetate, manganous hydroxide, the ammonium dihydrogen phosphate of certain mass in molar ratio; then add in the ball grinder of prior water-soluble solution 5% sucrose; carry out ball milling 30min; after ball milling, slurry is put into chemical combination stove chemical combination 5min, obtain lithium ferric manganese phosphate presoma, then by presoma grinding, compressing tablet; under inert gas atmosphere protection; 650 DEG C of calcining 12h, cool to room temperature with the furnace, obtain the lithium ferric manganese phosphate positive electrode that carbon is coated.
Comparative example 1
1.0 ~ 1.2:0.45:0.55:1 weighs the lithium oxalate of certain mass, ferric acetate, manganese dioxide and diammonium hydrogen phosphate in molar ratio; then add in the ball grinder of prior water-soluble solution 4% lemon; carry out ball milling 30min; slurry after ball milling is put into a conventional oven and is carried out 10min oven dry, obtains lithium ferric manganese phosphate presoma, then by presoma grinding, compressing tablet; under inert gas atmosphere protection; 700 DEG C of calcining 12h, cool to room temperature with the furnace, obtain the lithium ferric manganese phosphate positive electrode that carbon is coated.
Comparative example 2
1.0 ~ 1.2:0.55:0.45:1 weighs the lithium acetate of certain mass, ferric acetate, manganese oxalate and ammonium dihydrogen phosphate in molar ratio; then add in the beaker of prior water-soluble solution 5% soluble starch; carry out stirring 30min; after stirring, slurry is put into chemical combination stove chemical combination 5min, obtain lithium ferric manganese phosphate presoma, then by presoma grinding, compressing tablet; under inert gas atmosphere protection; 600 DEG C of calcining 20h, cool to room temperature with the furnace, obtain the lithium ferric manganese phosphate positive electrode that carbon is coated.
Claims (8)
1. a lithium ion battery positive pole material phosphoric acid ferrimanganic lithium, it is characterized in that, comprise following component: Li source compound, Fe source compound, manganese source compound, P source compound, in lithium: iron: manganese: phosphorus mol ratio is that the ratio of 1.0 ~ 1.2:0.1 ~ 0.9:0.1 ~ 0.9:1 carries out each compound;
Lithium ion battery positive pole material phosphoric acid ferrimanganic lithium according to claim 1, is characterized in that, described Li source compound is at least one in lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate.
2. according to the lithium ion battery positive pole material phosphoric acid ferrimanganic lithium described in claims 1, it is characterized in that, described Fe source compound is at least one in ferric phosphate, iron hydroxide, ferric acetate.
3. according to the lithium ion battery positive pole material phosphoric acid ferrimanganic lithium described in claims 1, it is characterized in that, described manganese source compound is at least one in manganese oxalate, the sub-manganese of acetic acid, manganese dioxide, manganous hydroxide.
4. according to the lithium ion battery positive pole material phosphoric acid ferrimanganic lithium described in claims 1, it is characterized in that, it is characterized in that, described P source compound is at least one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid.
5. a preparation method for lithium ion battery positive pole material phosphoric acid ferrimanganic lithium, is characterized in that,
The thing carbon-source cpd of organic solvent dissolution 2wt% ~ 5wt% in ball grinder, then the mixture of Li source compound, Fe source compound, manganese source compound and P source compound is put into ball grinder carry out ball milling 1 ~ 5h;
Ball milling disposed slurry is put into chemical combination stove and carries out the process of 2-30min chemical combination, obtain presoma;
Take out presoma grinding, compressing tablet;
In inert gas atmosphere, be heated to 600 ~ 900 DEG C, and continue calcining 5 ~ 20h at 600 ~ 900 DEG C, obtain the lithium ion battery positive pole material phosphoric acid ferrimanganic lithium that carbon is coated.
6. according to the preparation method of the lithium ion battery positive pole material phosphoric acid ferrimanganic lithium described in claims 6, it is characterized in that, described carbon-source cpd is at least one in sucrose, glucose, soluble starch, citric acid.
7., according to the preparation method of the lithium ion battery positive pole material phosphoric acid ferrimanganic lithium described in claims 6, it is characterized in that, described organic solvent is selected from the one in industrial alcohol, absolute ethyl alcohol, acetone, deionized water.
8., according to the preparation method of the lithium ion battery positive pole material phosphoric acid ferrimanganic lithium described in claims 6, it is characterized in that, described inert gas is selected from the one in argon gas, helium, nitrogen.
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| CN201410505399.9A CN104347875A (en) | 2014-09-28 | 2014-09-28 | Positive electrode material lithium iron manganese phosphate of lithium-ion battery and a preparing method of positive electrode material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329867A (en) * | 2015-11-11 | 2016-02-17 | 浙江兴海能源科技有限公司 | High-compaction preparation method of lithium ferric manganese phosphate |
| CN105355885A (en) * | 2015-11-26 | 2016-02-24 | 中南大学 | Synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C |
| CN105406067A (en) * | 2015-12-08 | 2016-03-16 | 山东精工电子科技有限公司 | Preparation method for titanium oxide modified lithium manganese iron phosphate positive electrode material |
| CN105977456A (en) * | 2015-03-12 | 2016-09-28 | 中国科学院成都有机化学有限公司 | Solid-phase synthesis method for preparing LiMn1-xFexPO4/C composite material |
| CN106904588A (en) * | 2017-03-22 | 2017-06-30 | 江苏元景锂粉工业有限公司 | A kind of lithium ion battery with high energy density positive electrode and preparation method thereof |
| CN107834025A (en) * | 2017-07-08 | 2018-03-23 | 郑春燕 | A kind of compound lithium ion electrode material |
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| CN102874789A (en) * | 2012-10-22 | 2013-01-16 | 苏州大学 | Lithium ion battery anode material lithium iron manganese phosphate and preparation method thereof |
| CN104037413A (en) * | 2014-06-19 | 2014-09-10 | 合肥国轩高科动力能源股份公司 | Preparation method of positive electrode material (carbon-coated iron-manganese-lithium phosphate) of lithium ion battery |
-
2014
- 2014-09-28 CN CN201410505399.9A patent/CN104347875A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874789A (en) * | 2012-10-22 | 2013-01-16 | 苏州大学 | Lithium ion battery anode material lithium iron manganese phosphate and preparation method thereof |
| CN104037413A (en) * | 2014-06-19 | 2014-09-10 | 合肥国轩高科动力能源股份公司 | Preparation method of positive electrode material (carbon-coated iron-manganese-lithium phosphate) of lithium ion battery |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105977456A (en) * | 2015-03-12 | 2016-09-28 | 中国科学院成都有机化学有限公司 | Solid-phase synthesis method for preparing LiMn1-xFexPO4/C composite material |
| CN105329867A (en) * | 2015-11-11 | 2016-02-17 | 浙江兴海能源科技有限公司 | High-compaction preparation method of lithium ferric manganese phosphate |
| CN105355885A (en) * | 2015-11-26 | 2016-02-24 | 中南大学 | Synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C |
| CN105406067A (en) * | 2015-12-08 | 2016-03-16 | 山东精工电子科技有限公司 | Preparation method for titanium oxide modified lithium manganese iron phosphate positive electrode material |
| CN106904588A (en) * | 2017-03-22 | 2017-06-30 | 江苏元景锂粉工业有限公司 | A kind of lithium ion battery with high energy density positive electrode and preparation method thereof |
| CN106904588B (en) * | 2017-03-22 | 2019-05-24 | 江苏元景锂粉工业有限公司 | A kind of lithium ion battery with high energy density positive electrode and preparation method thereof |
| CN107834025A (en) * | 2017-07-08 | 2018-03-23 | 郑春燕 | A kind of compound lithium ion electrode material |
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Application publication date: 20150211 |