CN105609763A - Rare earth Y doped lithium iron phosphate electrode material and preparation method thereof - Google Patents
Rare earth Y doped lithium iron phosphate electrode material and preparation method thereof Download PDFInfo
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- CN105609763A CN105609763A CN201510978190.9A CN201510978190A CN105609763A CN 105609763 A CN105609763 A CN 105609763A CN 201510978190 A CN201510978190 A CN 201510978190A CN 105609763 A CN105609763 A CN 105609763A
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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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- 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
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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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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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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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention provides a rare earth Y doped lithium iron phosphate electrode material and a preparation method thereof. According to the preparation method, in the preparation process of the lithium iron phosphate anode material, the rare earth Y element is doped, a lithium iron phosphate composite compound is prepared and formed through a ball-milling and vacuum high-temperature calcination process, the lattice constant of the lithium iron phosphate material is increased through the doped rare earth element, the Li<+> embedding and emigration capacity is improved, the charging and discharging stability of the material is improved, the problem of low electronic conductivity is overcome, and meanwhile, the crystallization is more complete, and particles are uniformer.
Description
Technical field
The present invention relates to a kind of electrode material, particularly the electrode material of a kind of rare earth doped Y and preparation method thereof, belong to field of batteries.
Background technology
20th century, the mid-80 started, and due to portability, the miniaturization of the devices such as Voice & Video, promoted the transition from dry cell to rechargeable battery of battery as power supply, promoted the high capacity of nickel-cadmium cell simultaneously. Although the energy density of nickel-cadmium cell constantly improves, reached the limit of its technology to the nineties in 20th century, be necessary to develop new high performance rechargeable battery. In addition owing to worrying the impact of cadmium on environment, America and Europe has formulated strict recycling policy to nickel-cadmium cell. Under such background, develop lithium ion battery. Lithium ion battery, because of the ideal source that it has that specific energy is large, self discharge is little, has extended cycle life, lightweight and advantages of environment protection becomes portable type electronic product, is also the first-selected power supply of following electric automobile and hybrid-electric car. Therefore, lithium ion battery and associated materials thereof have become one of study hotspot of countries in the world scientific research personnel.
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 the shortcoming that some are 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, reported polyanion type compound L iFePO4Have good performance as anode material for lithium-ion batteries, 1997, the people such as Padhit proposed olivine-type LiFePO4Positive electrode, the advantages such as it possesses raw material wide material sources, 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. But LiFePO4The shortcoming of positive electrode is that electronic conductivity is lower, and the heavy-current discharge performance of material is poor.
Rare earth metal claims again rare earth element, it is the general name of scandium, yttrium, 17 kinds of elements of group of the lanthanides in periodic table of elements III B family, rare earth metal is not subject to the impact of conduction electron and contiguous dot matrix to a great extent, in extranuclear electron layer, 4f shell is discontented, there is magnetic moment, 4f shell " buried " is in atom, and these unique character have a wide range of applications rare earth metal in a lot of fields.
The present invention is in lithium iron phosphate positive material preparation process, and rare earth doped Y element, forms LiFe1-xYxPO4Compound, the rare earth element of doping does not change raw-material crystal structure, only changes its lattice parameter c, because rare earth atom radius is larger, can make C increase, and means that interlamellar spacing becomes large, so also just has Li faster+Embed and the ability of moving out the more excellent stability that discharges and recharges; In addition, adding of rare earth, can make crystallization more complete, and particle is more even, overcomes the problem that electronic conductivity is lower.
Summary of the invention
The object of this invention is to provide iron phosphate lithium electrode material of a kind of rare earth doped Y and preparation method thereof, this preparation method comprises the steps:
(1) get appropriate chemical pure LiAc, NH4H2PO4、FeC2O4?2H2O and Y, by it according to Li:P:Fe:Y=1:1:1-x:x(0.01≤X≤0.1) ratio mix;
(2) get again a ball grinder, the raw material preparing is poured in ball grinder, and add appropriate sucrose and steel ball, fill tank with acetone, after covering tightly, place on planetary ball mill;
(3) start planetary ball mill, after ball milling a period of time, open ball grinder, pour out supernatant liquid, then take out lower metal powder;
Take out metal fine powder by naturally drying;
(5) the metal fine powder drying is packed in quartz glass tube, and carry out vacuum seal;
(6) the quartz glass tube of sealing is dropped in water, whether inspection has bubble to emerge, if do not see bubble, shows that air-tightness is good;
(7) again the quartz glass tube of sealing is put into high temperature furnace, calcine;
(8) after calcining, take out quartz glass tube, smash after cooling glass tube, collection powder obtains the iron phosphate lithium electrode material of a kind of rare earth doped Y.
Preferentially, step (2) in, ratio of grinding media to material is 20:1.
Preferentially, step (3) in, planetary type ball-milling motor speed control 300-400r/min operation, the time of ball milling is 4-6h.
Preferentially, step (7) in, high-temperature calcination temperature is 700-900 DEG C, the time is controlled at 8-10h.
The present invention has following advantages and characteristic:
(1) the electronic conductivity of modification rear electrode material is better;
(2) preparation technology is simple, easy to operate;
(3) flow process is short, is easy to realize industrialization.
Embodiment mono-:
Get appropriate chemical pure LiAc, NH4H2PO4、FeC2O4?2H2O and Y are as raw material, according to Li0.99FeY0.01PO4Atomic ratio batching, taking out the raw mixture preparing of 5g pours in a ball grinder, and add the sucrose of 2g and the steel ball of 100g, pour again acetone soln into, after submergence ball grinder, cover is covered tightly, put into planetary ball mill and carry out ball milling, ball milling speed arranges 300r/min, after ball milling 6h, take out ball grinder, alloy powder is taken out, putting into a smooth container dries, again the powder drying is packed in quartz glass tube, and carry out vacuum seal, the quartz glass tube of good seal is dropped in water, if there is no bubble, show that sealing is good, again quartz glass tube being put into the high temperature furnace of 700 DEG C calcines, after calcining 10h, take out quartz glass tube, smash after cooling glass tube, collect the iron phosphate lithium electrode material that powder obtains a kind of rare earth doped Y.
Embodiment bis-:
Get appropriate chemical pure LiAc, NH4H2PO4、FeC2O4?2H2O and Y are as raw material, according to Li0.95FeY0.05PO4Atomic ratio batching, taking out the raw mixture preparing of 10g pours in a ball grinder, and add the sucrose of 5g and the steel ball of 400g, pour again acetone soln into, after submergence ball grinder, cover is covered tightly, put into planetary ball mill and carry out ball milling, ball milling speed arranges 400r/min, after ball milling 4h, take out ball grinder, alloy powder is taken out, putting into a smooth container dries, again the powder drying is packed in quartz glass tube, and carry out vacuum seal, the quartz glass tube of good seal is dropped in water, if there is no bubble, show that sealing is good, again quartz glass tube being put into the high temperature furnace of 800 DEG C calcines, after calcining 9h, take out quartz glass tube, smash after cooling glass tube, collect the iron phosphate lithium electrode material that powder obtains a kind of rare earth doped Y.
Embodiment tri-:
Get appropriate chemical pure LiAc, NH4H2PO4、FeC2O4?2H2O and Y are as raw material, according to Li0.9FeY0.1PO4Atomic ratio batching, taking out the raw mixture preparing of 10g pours in a ball grinder, and add the sucrose of 5g and the steel ball of 400g, pour again acetone soln into, after submergence ball grinder, cover is covered tightly, put into planetary ball mill and carry out ball milling, ball milling speed arranges 400r/min, after ball milling 5h, take out ball grinder, alloy powder is taken out, putting into a smooth container dries, again the powder drying is packed in quartz glass tube, and carry out vacuum seal, the quartz glass tube of good seal is dropped in water, if there is no bubble, show that sealing is good, again quartz glass tube being put into the high temperature furnace of 900 DEG C calcines, after calcining 8h, take out quartz glass tube, smash after cooling glass tube, collect the iron phosphate lithium electrode material that powder obtains a kind of rare earth doped Y.
Claims (4)
1. an iron phosphate lithium electrode material of rare earth doped Y, is characterized in that, the preparation method of this electrode material comprises the steps:
(1) get appropriate chemical pure LiAc, NH4H2PO4、FeC2O4?2H2O and Y, by it according to Li:P:Fe:Y=1:1:1-x:x(0.01≤X≤0.1) ratio mix;
(2) get again a ball grinder, the raw material preparing is poured in ball grinder, and add appropriate sucrose and steel ball, fill tank with acetone, after covering tightly, place on planetary ball mill;
(3) start planetary ball mill, after ball milling a period of time, open ball grinder, pour out supernatant liquid, then take out lower metal powder;
Take out metal fine powder by naturally drying;
(5) the metal fine powder drying is packed in quartz glass tube, and carry out vacuum seal;
(6) the quartz glass tube of sealing is dropped in water, whether inspection has bubble to emerge, if do not see bubble, shows that air-tightness is good;
(7) again the quartz glass tube of sealing is put into high temperature furnace, calcine;
(8) after calcining, take out quartz glass tube, smash after cooling glass tube, collection powder obtains the iron phosphate lithium electrode material of a kind of rare earth doped Y.
2. the iron phosphate lithium electrode material of a kind of rare earth doped Y according to claim 1, is characterized in that, step (2) in, ratio of grinding media to material is 20:1.
3. the iron phosphate lithium electrode material of a kind of rare earth doped Y according to claim 1, is characterized in that, step (3) in, planetary type ball-milling motor speed control 300-400r/min operation, the time of ball milling is 4-6h.
4. the iron phosphate lithium electrode material of a kind of rare earth doped Y according to claim 1, is characterized in that, step (7) in, high-temperature calcination temperature is 700-900 DEG C, the time is controlled at 8-10h.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106315537A (en) * | 2016-08-04 | 2017-01-11 | 陕西科技大学 | Preparation method of lithium iron phosphate powder |
CN107464925A (en) * | 2017-08-02 | 2017-12-12 | 商丘职业技术学院 | A kind of lithium battery and power device |
CN108615883A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of Li of doping Yb, Gd1-(x+y)FeYbxGdyPO4Combination electrode material |
CN108615858A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of combination electrode material and its technique of doping Pr, Sm |
CN108615881A (en) * | 2016-12-11 | 2018-10-02 | 张彩缘 | A kind of Li1-(x+y)FeHOxLayPO4Combination electrode material and its technique |
CN108615882A (en) * | 2016-12-11 | 2018-10-02 | 张彩缘 | A kind of Li1-(x+y)FeCexNdyPO4Combination electrode material |
CN108609597A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of li-ion electrode materials of rare earth doped terbium, dysprosium |
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CN101121508A (en) * | 2006-08-08 | 2008-02-13 | 新疆大学 | Method for synthesizing lithium iron phosphate battery anode material by microwave |
CN101546831A (en) * | 2008-03-28 | 2009-09-30 | 潘树明 | Lithium ion battery anode material composite lithium iron phosphate and four-step synthesis and preparation process thereof |
US20110037030A1 (en) * | 2007-12-06 | 2011-02-17 | Sud-Chemie Ag | Nanoparticulate composition and method for its production |
CN102082266A (en) * | 2010-12-28 | 2011-06-01 | 陕西科技大学 | Solid-phase preparation method of composite coated lithium iron phosphate anode material |
CN102104148A (en) * | 2010-12-31 | 2011-06-22 | 北京中科浩运科技有限公司 | Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof |
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2015
- 2015-12-23 CN CN201510978190.9A patent/CN105609763A/en active Pending
Patent Citations (5)
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CN101121508A (en) * | 2006-08-08 | 2008-02-13 | 新疆大学 | Method for synthesizing lithium iron phosphate battery anode material by microwave |
US20110037030A1 (en) * | 2007-12-06 | 2011-02-17 | Sud-Chemie Ag | Nanoparticulate composition and method for its production |
CN101546831A (en) * | 2008-03-28 | 2009-09-30 | 潘树明 | Lithium ion battery anode material composite lithium iron phosphate and four-step synthesis and preparation process thereof |
CN102082266A (en) * | 2010-12-28 | 2011-06-01 | 陕西科技大学 | Solid-phase preparation method of composite coated lithium iron phosphate anode material |
CN102104148A (en) * | 2010-12-31 | 2011-06-22 | 北京中科浩运科技有限公司 | Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106315537A (en) * | 2016-08-04 | 2017-01-11 | 陕西科技大学 | Preparation method of lithium iron phosphate powder |
CN108615881A (en) * | 2016-12-11 | 2018-10-02 | 张彩缘 | A kind of Li1-(x+y)FeHOxLayPO4Combination electrode material and its technique |
CN108615882A (en) * | 2016-12-11 | 2018-10-02 | 张彩缘 | A kind of Li1-(x+y)FeCexNdyPO4Combination electrode material |
CN108615883A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of Li of doping Yb, Gd1-(x+y)FeYbxGdyPO4Combination electrode material |
CN108615858A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of combination electrode material and its technique of doping Pr, Sm |
CN108609597A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of li-ion electrode materials of rare earth doped terbium, dysprosium |
CN107464925A (en) * | 2017-08-02 | 2017-12-12 | 商丘职业技术学院 | A kind of lithium battery and power device |
CN107464925B (en) * | 2017-08-02 | 2020-08-18 | 商丘职业技术学院 | Lithium battery and power utilization device |
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Application publication date: 20160525 |