CN105428650A - Novel polyanionic-based electrode material and preparation method thereof - Google Patents
Novel polyanionic-based electrode material and preparation method thereof Download PDFInfo
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- CN105428650A CN105428650A CN201510977540.XA CN201510977540A CN105428650A CN 105428650 A CN105428650 A CN 105428650A CN 201510977540 A CN201510977540 A CN 201510977540A CN 105428650 A CN105428650 A CN 105428650A
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- electrode material
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- novel polyanionic
- novel
- polyanionic
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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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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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Abstract
The invention provides a novel polyanionic-based electrode material and a preparation method thereof. The novel polyanionic-based electrode material doped with Ni can be obtained according to the following steps of firstly mixing raw materials of Li<2>CO<3>, FeC<2>O<4>.2H<2>O, NH<4>H<2>PO<4> and NiO<3> according to certain proportions; secondly, carrying out ball grinding on the mixed raw materials and sucrose under the protection atmosphere of acetone; and drying the ball-grinded metal powder after ball grinding; and finally, carrying out high-temperature calcination under the protection atmosphere of argon and cooling the metal powder.
Description
Technical field
The present invention relates to a kind of electrode material, particularly a kind of other metallic atoms that adulterate improve a kind of method of polyanionic electrode material, belong to field of batteries.
Background technology
Lithium battery is a class is negative material, the battery using non-aqueous electrolytic solution by lithium metal or lithium alloy.Within 1912, lithium metal battery is proposed by GilbertN.Lewis the earliest and studies.During 20 century 70, M.S.Whittingham proposes and the lithium ion battery that begins one's study.Because the chemical characteristic of lithium metal is very active, make the processing of lithium metal, preservation, use, very high to environmental requirement.So lithium battery is not applied for a long time.Along with the development of science and technology, present lithium battery becomes main flow.But lithium battery majority is secondary cell, also once property battery.Life-span and the fail safe of the secondary cell of minority are poor.Afterwards, it took Carbon Materials as negative pole that Sony corporation of Japan has been invented, and to make the lithium battery of positive pole containing the compound of lithium, in charge and discharge process, did not have lithium metal, only had lithium ion, Here it is lithium ion battery.When charging to battery, the positive pole of battery has lithium ion to generate, the lithium ion of generation through electrolyte movement to negative pole.And be layer structure as the carbon of negative pole, it has a lot of micropore, and the lithium ion reaching negative pole is just embedded in the micropore of carbon-coating, and the lithium ion of embedding is more, and charging capacity is higher.Equally, when discharging to battery (we use the process of battery), the lithium ion be embedded in negative pole carbon-coating is deviate from, and move back again positive pole.
Anode material for lithium-ion batteries mainly contains inorganic metal compound material, organic molecule material and polymeric material three major types.Wherein inorganic metal compound material is by the metal sulfide of the first generation, develop into the metal oxide of the second generation, but above-mentioned two class positive electrodes have some shortcomings being difficult to overcome separately, as on the low side in specific capacity, price is higher, cycle performance is not very good and potential safety hazard factor is relatively outstanding etc.In recent years, polyanionic compound L iFePO is reported
4have good performance as anode material for lithium-ion batteries, 1997, the people such as Padhit proposed olivine-type LiFePO
4positive electrode, it possesses the advantages such as raw material sources is extensive, with low cost, pollution-free, security performance is high, resulting materials no hygroscopicity, and it has higher specific capacity, and (theoretical specific capacity is 170mAh/g, specific energy is 550Wh/kg) and higher operating voltage (3.4V), along with the rising of temperature, the specific capacity of battery also can significantly improve, and is more satisfactory a kind of positive electrode.
Polyanionic compound is a series of general names containing the compound of tetrahedron or octahedra anion structure unit.These construction units also form the space occupied by other metal ion of higher coordination by the three-dimensional net structure that strong covalent bond is linked to be, and make polyanionic compound positive electrode have the crystal phase structure different with metal oxide cathode material and the various outstanding performance by structures shape.This series material has two outstanding advantages, and the crystal framework structure of material is stablized, even if a large amount of lithium ion deintercalation, some metallizing thing type positive electrodes have larger difference; The second, be easy to the discharge potential platform of modulation material.But it is lower that the shortcoming of polyanionic compound is electronic conductivity, the heavy-current discharge performance of material is poor.
In order to overcome the problems referred to above, the present invention is at LiFePO
4preparation process in, add NiO
3, then make LiFePO by ball-milling technology, high temperature solid-state method
4adulterate in lattice a small amount of W metal ion, improves the conduction rate of electrode material, have a good application prospect in the electrode material of preparation.
Summary of the invention
The object of this invention is to provide a kind of novel polyanionic electrode material and preparation method thereof.This preparation method comprises the steps:
(1) get appropriate FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and NiO
3, by it according to Li:P:Fe:Ni=1:1:1-x:x(0.01≤X≤0.1) ratio mixing;
(2) get a ball grinder again, the raw material of appropriate mixing and sucrose are poured in tank, then drop into the steel ball of certain mass ratio, then fill tank with acetone, after being covered tightly by lid, place ball milling on ball mill;
(3) after ball milling terminates, open ball grinder, pour out supernatant liquid, then take out lower metal powder;
(4) the metal dust poured out fully is dried;
Again by dry powder place in a high-temperature calcination stove;
(6), after high-temperature calcination stove being full of argon gas, calcine;
(7) the powder through calcination processing is taken out, cool to obtain a kind of novel polyanionic electrode material of Ni doped.
Preferentially, step (1) in, FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and NiO
3purity be chemical pure.
Preferentially, step (2) in, ratio of grinding media to material is 20:1, and planetary ball mill speeds control 300-400r/min runs.
Preferentially, step (3) in, the time of carrying out ball milling with planetary ball mill is 4-6h.
Preferentially, step (6) in, high-temperature calcination temperature is 700-900 DEG C, and time controling is at 8-10h.
The present invention has following advantages and characteristic:
(1) the electronic conductivity of modified electrode material is better;
(2) preparation technology is simple, easy to operate;
(3) flow process is short, is easy to realize industrialization.
Embodiment one:
Get appropriate FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and NiO
3, its ratio according to Li:P:Fe:Ni=1:1:0.99:0.1 is mixed, get a ball grinder again, the raw material of the mixing of appropriate 5g and the sucrose of 3g are poured in tank, drop into the steel ball of 200g again, then tank is filled with acetone soln, lid is covered tightly ball milling on rear placement ball mill, mill speed arranges 300r/min, after ball milling 6h, stop ball milling, open ball grinder, pour out supernatant liquid, take out lower metal powder again, metal dust is fully dried, again by dry powder place in a high-temperature calcination stove, after high-temperature calcination stove is full of argon gas, calcine at 700 DEG C, take out after 10h and cool to obtain a kind of novel polyanionic electrode material of Ni doped.
Embodiment two:
Get appropriate FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and NiO
3, its ratio according to Li:P:Fe:Ni=1:1:0.95:0.05 is mixed, get a ball grinder again, the raw material of the mixing of appropriate 10g and the sucrose of 5g are poured in tank, drop into the steel ball of 400g again, then tank is filled with acetone soln, lid is covered tightly ball milling on rear placement ball mill, mill speed arranges 400r/min, after ball milling 4h, stop ball milling, open ball grinder, pour out supernatant liquid, take out lower metal powder again, metal dust is fully dried, again by dry powder place in a high-temperature calcination stove, after high-temperature calcination stove is full of argon gas, calcine at 80 DEG C, take out after 9h and cool to obtain a kind of novel polyanionic electrode material of Ni doped.
Embodiment three:
Get appropriate FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and NiO
3, its ratio according to Li:P:Fe:Ni=1:1:0.9:0.1 is mixed, get a ball grinder again, the raw material of the mixing of appropriate 10g and the sucrose of 5g are poured in tank, drop into the steel ball of 400g again, then tank is filled with acetone soln, lid is covered tightly ball milling on rear placement ball mill, mill speed arranges 400r/min, after ball milling 5h, stop ball milling, open ball grinder, pour out supernatant liquid, take out lower metal powder again, metal dust is fully dried, again by dry powder place in a high-temperature calcination stove, after high-temperature calcination stove is full of argon gas, calcine at 900 DEG C, take out after 8h and cool to obtain a kind of novel polyanionic electrode material of Ni doped.
Claims (5)
1. a novel polyanionic electrode material for Ni doped, it is characterized in that, the preparation method of this electrode material comprises the steps:
(1) get appropriate FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and NiO
3, by it according to Li:P:Fe:Ni=1:1:1-x:x(0.01≤X≤0.1) ratio mixing;
(2) get a ball grinder again, the raw material of appropriate mixing and sucrose are poured in tank, then drop into the steel ball of certain mass ratio, then fill tank with acetone, after being covered tightly by lid, place ball milling on ball mill;
(3) after ball milling terminates, open ball grinder, pour out supernatant liquid, then take out lower metal powder;
(4) the metal dust poured out fully is dried;
Again by dry powder place in a high-temperature calcination stove;
(6), after high-temperature calcination stove being full of argon gas, calcine;
(7) the powder through calcination processing is taken out, cool to obtain a kind of LiFe
1-xni
xpO
4electrode material.
2. the novel polyanionic electrode material of a kind of Ni doped according to claim 1, is characterized in that, step (1) in, FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and NiO
3purity be chemical pure.
3. the novel polyanionic electrode material of a kind of Ni doped according to claim 1, is characterized in that, step (2) in, ratio of grinding media to material is 20:1, and planetary ball mill speeds control 300-400r/min runs.
4. the novel polyanionic electrode material of a kind of Ni doped according to claim 1, is characterized in that, step (3) in, the time of carrying out ball milling with planetary ball mill is 4-6h.
5. the novel polyanionic electrode material of a kind of Ni doped according to claim 1, is characterized in that, step (6) in, high-temperature calcination temperature is 700-900 DEG C, and time controling is at 8-10h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510977540.XA CN105428650A (en) | 2015-12-23 | 2015-12-23 | Novel polyanionic-based electrode material and preparation method thereof |
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|---|---|---|---|
| CN201510977540.XA CN105428650A (en) | 2015-12-23 | 2015-12-23 | Novel polyanionic-based electrode material and preparation method thereof |
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|---|---|
| CN105428650A true CN105428650A (en) | 2016-03-23 |
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ID=55506694
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224226A (en) * | 2013-04-15 | 2013-07-31 | 宜兴奕润新能源科技有限公司 | Nano-lithium iron phosphate material suitable for high rate power battery and preparation method thereof |
| CN104393291A (en) * | 2014-11-10 | 2015-03-04 | 三峡大学 | LiFePO4 positive electrode material modified jointly by doping and coating and preparation method thereof |
| CN104701503A (en) * | 2013-12-09 | 2015-06-10 | 青岛平度市旧店金矿 | Process for preparing iron site doped LiFePO4/C through spray drying method |
-
2015
- 2015-12-23 CN CN201510977540.XA patent/CN105428650A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224226A (en) * | 2013-04-15 | 2013-07-31 | 宜兴奕润新能源科技有限公司 | Nano-lithium iron phosphate material suitable for high rate power battery and preparation method thereof |
| CN104701503A (en) * | 2013-12-09 | 2015-06-10 | 青岛平度市旧店金矿 | Process for preparing iron site doped LiFePO4/C through spray drying method |
| CN104393291A (en) * | 2014-11-10 | 2015-03-04 | 三峡大学 | LiFePO4 positive electrode material modified jointly by doping and coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 章兴石，肖方明，王英等: "镍离子掺杂对LiFePO4/C电化学性能的影响", 《电源技术》 * |
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