CN105428651A - Rare-earth cerium-doped lithium iron phosphate composite electrode material - Google Patents

Rare-earth cerium-doped lithium iron phosphate composite electrode material Download PDF

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Publication number
CN105428651A
CN105428651A CN201510978255.XA CN201510978255A CN105428651A CN 105428651 A CN105428651 A CN 105428651A CN 201510978255 A CN201510978255 A CN 201510978255A CN 105428651 A CN105428651 A CN 105428651A
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electrode material
glass tube
rare earth
earth cerium
quartz glass
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郑春燕
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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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a rare-earth cerium-doped lithium iron phosphate composite electrode material and a preparation method thereof. According to the preparation method, a cerium element is doped in the process of preparing a lithium iron phosphate material through ball-milling and vacuum high-temperature calcining technologies, so as to form a lithium iron phosphate mixed compound. The lattice constant of the lithium iron phosphate material is increased by the doped rare-earth element; the Li<+> intercalation and deintercalation capabilities are improved; the charge-discharge stability of the material is improved; and the problem of low electronic conductivity is solved.

Description

A kind of LiFePO4 combination electrode material of rare earth cerium doping
Technical field
The present invention relates to a kind of electrode material, particularly a kind of electrode material and preparation method thereof of rare earth cerium doping, belongs 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, facilitated battery as power supply from dry cell to the transition of rechargeable battery, in this context, have developed lithium ion battery.Lithium ion battery because of its have that specific energy is large, self discharge is little, have extended cycle life, lightweight and advantages of environment protection and become the ideal source of portable type electronic product, be also the first-selected power supply of following electric automobile and hybrid-electric car.
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.But LiFePO 4the shortcoming of positive electrode is that electronic conductivity is lower, and the heavy-current discharge performance of material is poor.
Rare earth metal is also known as rare earth element, it is the general name of scandium, yttrium, group of the lanthanides 17 kinds of elements in the periodic table of elements III B race, rare earth metal is not to a great extent by the impact of conduction electron with contiguous dot matrix, in extranuclear electron layer, 4f shell is discontented with, there is magnetic moment, 4f shell " buried " is in atom, and the character of these uniquenesses makes rare earth metal have a wide range of applications in a lot of fields.
The present invention is in lithium iron phosphate positive material preparation process, and rare earth doped Ce elements, forms LiFe 1-xce xpO 4compound, 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 comparatively large, C can be made to increase, and namely means that interlamellar spacing becomes large, so just has Li faster yet +embed and ability of moving out, more excellent stable charge/discharge; In addition, adding of rare earth, crystallization can be made more complete, particle evenly, overcome the problem that electronic conductivity is lower.
Summary of the invention
LiFePO4 combination electrode material that the object of this invention is to provide a kind of rare earth cerium doping and preparation method thereof, this preparation method comprises the steps:
(1) get appropriate chemical pure LiAc, NH 4h 2pO 4, FeC 2o 42H 2o and Ce, by it according to Li:P:Fe:Ce=1:1:1-x:x(0.01≤X≤0.1) ratio mixing;
(2) the raw material prepared 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 dried is loaded 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 glass tube after cooling, collect the LiFePO4 combination electrode material that namely powder obtains a kind of rare earth cerium doping.
Preferentially, step (2) in, ratio of grinding media to material is 20:1.
Preferentially, step (3) in, planetary ball mill speeds control 300-400r/min runs, and the time of ball milling is 4-6h.
Preferentially, step (7) 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 chemical pure LiAc, NH 4h 2pO 4, FeC 2o 42H 2o and Ce as raw material, according to Li 0.99feCe 0.01pO 4atomic ratio batching, the raw mixture prepared taking out 5g is poured in a ball grinder, and add the sucrose of 2g and the steel ball of 100g, pour acetone soln into again, 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, put into a smooth container to dry, again the powder dried is loaded 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 the high temperature furnace that quartz glass tube puts into 700 DEG C is calcined, after calcining 10h, take out quartz glass tube, smash glass tube after cooling, collect the LiFePO4 combination electrode material that namely powder obtains a kind of rare earth cerium doping.
Embodiment two:
Get appropriate chemical pure LiAc, NH 4h 2pO 4, FeC 2o 42H 2o and Ce as raw material, according to Li 0.95feCe 0.05pO 4atomic ratio batching, the raw mixture prepared taking out 10g is poured in a ball grinder, and add the sucrose of 5g and the steel ball of 400g, pour acetone soln into again, 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, put into a smooth container to dry, again the powder dried is loaded 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 the high temperature furnace that quartz glass tube puts into 800 DEG C is calcined, after calcining 9h, take out quartz glass tube, smash glass tube after cooling, collect the LiFePO4 combination electrode material that namely powder obtains a kind of rare earth cerium doping.
Embodiment three:
Get appropriate chemical pure LiAc, NH 4h 2pO 4, FeC 2o 42H 2o and Ce as raw material, according to Li 0.9feCe 0.1pO 4atomic ratio batching, the raw mixture prepared taking out 10g is poured in a ball grinder, and add the sucrose of 5g and the steel ball of 400g, pour acetone soln into again, 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, put into a smooth container to dry, again the powder dried is loaded 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 the high temperature furnace that quartz glass tube puts into 900 DEG C is calcined, after calcining 8h, take out quartz glass tube, smash glass tube after cooling, collect the LiFePO4 combination electrode material that namely powder obtains a kind of rare earth cerium doping.

Claims (4)

1. a LiFePO4 combination electrode material for rare earth cerium doping, is characterized in that, the preparation method of this electrode material comprises the steps:
(1) get appropriate chemical pure LiAc, NH 4h 2pO 4, FeC 2o 42H 2o and Ce, by it according to Li:P:Fe:Ce=1:1:1-x:x(0.01≤X≤0.1) ratio mixing;
(2) the raw material prepared 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 dried is loaded 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 glass tube after cooling, collect the LiFePO4 combination electrode material that namely powder obtains a kind of rare earth cerium doping.
2. the LiFePO4 combination electrode material of a kind of rare earth cerium doping according to claim 1, is characterized in that, step (2) in, ratio of grinding media to material is 20:1.
3. the LiFePO4 combination electrode material of a kind of rare earth cerium doping according to claim 1, is characterized in that, step (3) in, planetary ball mill speeds control 300-400r/min runs, and the time of ball milling is 4-6h.
4. the LiFePO4 combination electrode material of a kind of rare earth cerium doping according to claim 1, is characterized in that, step (7) in, high-temperature calcination temperature is 700-900 DEG C, and time controling is at 8-10h.
CN201510978255.XA 2015-12-23 2015-12-23 Rare-earth cerium-doped lithium iron phosphate composite electrode material Pending CN105428651A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107834025A (en) * 2017-07-08 2018-03-23 郑春燕 A kind of compound lithium ion electrode material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121510A (en) * 2007-09-07 2008-02-13 北京工业大学 Method for preparing Fe-position and P-position doping type lithium iron phosphate powder
CN101121508A (en) * 2006-08-08 2008-02-13 新疆大学 Method for synthesizing lithium iron phosphate battery anode material by microwave
EP2230706A1 (en) * 2009-03-15 2010-09-22 Ogron Bv Method for manufacturing rechargeable lithium batteries with thermally coated cathodes and anodes and the possibility of electrolyte exchange
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121508A (en) * 2006-08-08 2008-02-13 新疆大学 Method for synthesizing lithium iron phosphate battery anode material by microwave
CN101121510A (en) * 2007-09-07 2008-02-13 北京工业大学 Method for preparing Fe-position and P-position doping type lithium iron phosphate powder
EP2230706A1 (en) * 2009-03-15 2010-09-22 Ogron Bv Method for manufacturing rechargeable lithium batteries with thermally coated cathodes and anodes and the possibility of electrolyte exchange
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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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: 20160323