CN103594678A - Lithium iron phosphate electrode material - Google Patents

Lithium iron phosphate electrode material Download PDF

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Publication number
CN103594678A
CN103594678A CN201310501218.0A CN201310501218A CN103594678A CN 103594678 A CN103594678 A CN 103594678A CN 201310501218 A CN201310501218 A CN 201310501218A CN 103594678 A CN103594678 A CN 103594678A
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CN
China
Prior art keywords
electrode material
iron phosphate
nitrate
parts
metallic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310501218.0A
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Chinese (zh)
Inventor
丛国芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LIYANG DONGDA TECHNOLOGY TRANSFER CENTER Co Ltd
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LIYANG DONGDA TECHNOLOGY TRANSFER CENTER Co Ltd
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Publication date
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Priority to CN201310501218.0A priority Critical patent/CN103594678A/en
Publication of CN103594678A publication Critical patent/CN103594678A/en
Pending legal-status Critical Current

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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
    • H01M4/362—Composites
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/625—Carbon or graphite
    • 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
    • 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 discloses a lithium iron phosphate electrode material which is composed of the following components in parts by weight: 0-110 parts of Li1-xRx+yFe1-yPO4, 15-25 parts of metal compound and 5-15 parts of conducting assistant. The Li1-xRx+yFe1-yPO4 is an iron phosphate material containing substituting metal element R in both lithium position and iron position.

Description

A kind of iron phosphate lithium electrode material
Technical field
The invention belongs to electrode material field, particularly relate to a kind of iron phosphate lithium electrode material.
Background technology
The features such as lithium ion battery has that voltage is high, memory-less effect, energy density is high and cycle performance is good, have been widely used in the portable electric appts such as mobile phone, notebook computer, miniature camera.The performance of the positive electrode of lithium ion battery has determined the performance of lithium ion battery.At present, traditional anode material for lithium-ion batteries comprises cobalt acid lithium (LiCoO 2), lithium nickelate (LiNiO 2) and LiMn2O4 (LiMnO 2), because cobalt is poisonous and cobalt resource is limited, lithium nickelate preparation cycle performance and high-temperature behavior difficult, LiMn2O4 is poor.Therefore, these anode material for lithium-ion batteries cannot meet the requirement that lithium ion battery is high to specific capacity, the life-span is long, cost is low and environmental compatible aspect develops.
The LiFePO4 of olivine structural (LiFeP04) positive electrode is the positive electrode generally using in the industry at present, and this is that source is abundant, cheap because this material has, non-environmental-pollution, capacity are higher, good stability, the advantage such as safe and reliable.But compare with above-mentioned traditional material, the electronic conductivity of lithium iron phosphate positive material and ion diffusion rate are extremely low, thereby charge/discharge capacity is very low under high current density, can only under minimum electric current, discharge and recharge, this has just limited its application in practice greatly.Therefore the electronic conductivity that, how to improve LiFePO4 is current problem demanding prompt solution in the industry.
Summary of the invention
In order to overcome the defect existing in prior art, the invention provides a kind of iron phosphate lithium electrode material, adopt iron phosphate lithium electrode material of the present invention to be used as positive electrode, can improve electronic conductivity and example diffusion rate, thereby improve the performance of lithium battery.
The iron phosphate lithium electrode material that the present invention proposes, according to weight portion meter, has following component:
Li 1-xr x+yfe 1-ypO 490-110 part
Metallic compound 15-25 part
Conductive auxiliary agent 5-15 part
Wherein, Li 1-xr x+yfe 1-ypO 4for all contain the ferric phosphate material of displacement metallic element R in lithium position and iron position, any one metallic element or any two metallic elements of displacement metallic element R for selecting from the group being formed by aluminium, nickel, titanium and magnesium, and, 0.06≤x≤0.15,0.06≤y≤0.15;
Wherein, metallic compound is one or both that select in the group being comprised of ferric nitrate, nickel nitrate, cobalt nitrate, sodium nitrate, potassium nitrate, ferric acetate, nickel acetate, cobalt acetate, sodium sulphate, potassium sulfate, sodium carbonate, potash, sodium chloride and potassium chloride;
Wherein, conductive auxiliary agent is one or both that select in the group being comprised of acetylene black, electrically conductive graphite, conductive carbon black, sucrose and glucose.
Iron phosphate lithium electrode material of the present invention has following beneficial effect:
1. by adopting displacement metallic element to come part to replace lithium and the iron in LiFePO4, can improve the capacitance of iron phosphate lithium electrode material, and can also promote its charge-discharge performance;
2. add metallic compound, can reduce sintering temperature, the shortening sintering time of iron phosphate lithium electrode material in sintering process;
3. add conductive auxiliary agent, further improve the specific discharge capacity of iron phosphate lithium electrode material.
Embodiment
The iron phosphate lithium electrode material that the present invention proposes, according to weight portion meter, has following component:
Li 1-xr x+yfe 1-ypO 490-110 part
Metallic compound 15-25 part
Conductive auxiliary agent 5-15 part
Wherein, Li 1-xr x+yfe 1-ypO 4for all contain the ferric phosphate material of displacement metallic element R in lithium position and iron position, any one metallic element or any two metallic elements of displacement metallic element R for selecting from the group being formed by aluminium, nickel, titanium and magnesium, and, 0.06≤x≤0.15,0.06≤y≤0.15;
Wherein, metallic compound is one or both that select in the group being comprised of ferric nitrate, nickel nitrate, cobalt nitrate, sodium nitrate, potassium nitrate, ferric acetate, nickel acetate, cobalt acetate, sodium sulphate, potassium sulfate, sodium carbonate, potash, sodium chloride and potassium chloride;
Wherein, conductive auxiliary agent is one or both that select in the group being comprised of acetylene black, electrically conductive graphite, conductive carbon black, sucrose and glucose.
The manufacture method of introducing the iron phosphate lithium electrode material of the present invention's proposition below, described method in turn includes the following steps:
(1) according to previously described weight portion, by Li 1-xr x+yfe 1-ypO 4, metallic compound, conductive auxiliary agent join in stirred vessel, and be fully uniformly mixed after adding deionized water, thereby obtain mixture;
(2) mixture is put into drying box and be dried processing, wherein baking temperature is 120-140 ℃, and be 7-8 hour drying time;
(3) make powder, dried mixture is dropped in grinder and ground, obtain the powder of described mixture;
(4) described mixture powder is put into calciner and calcine, calcining heat is 350-400 ℃, and calcination time is 40-60 minute, finally obtains the sintering feed of described iron phosphate lithium electrode material.
Introduce the preferred embodiments of the present invention below:
The iron phosphate lithium electrode material that the present invention proposes, according to weight portion meter, has following component:
Li 1-xr x+yfe 1-ypO 4100 parts
20 parts of metallic compounds
10 parts of conductive auxiliary agents
Wherein, Li 1-xr x+yfe 1-ypO 4for all contain the ferric phosphate material of displacement metallic element R in lithium position and iron position, displacement metallic element R is titanium, x=0.1, y=0.1;
Wherein, metallic compound is cobalt nitrate or sodium chloride;
Wherein, conductive auxiliary agent is electrically conductive graphite or conductive carbon black;
The manufacture method of iron phosphate lithium electrode material of the present invention in turn includes the following steps:
(1) take the Li of 100 weight portions 1-xr x+yfe 1-ypO 4, the metallic compound of 20 weight portions and the conductive auxiliary agent of 10 weight portions join in stirred vessel, and be fully uniformly mixed after adding deionized water, thereby obtain mixture;
(2) mixture is put into drying box and be dried processing, wherein baking temperature is 130 ℃, and be 7 hours 20 minutes drying time;
(3) make powder, dried mixture is dropped in grinder and ground, obtain the powder of described mixture;
(4) described mixture powder is put into calciner and calcine, calcining heat is 380 ℃, and calcination time is 45 minutes, finally obtains the sintering feed of described iron phosphate lithium electrode material.
So far the present invention has been done to detailed explanation, but the embodiment of description above the preferred embodiments of the present invention just only, it is not intended to limit the present invention.Those skilled in the art can make any modification to the present invention, and protection scope of the present invention is limited to the appended claims.

Claims (3)

1. an iron phosphate lithium electrode material, according to weight portion meter, has following component:
Li 1-xr x+yfe 1-ypO 490-110 part;
Metallic compound 15-25 part;
Conductive auxiliary agent 5-15 part.
2. iron phosphate lithium electrode material as claimed in claim 1, is characterized in that:
Wherein, Li 1-xr x+yfe 1-ypO 4for all contain the ferric phosphate material of displacement metallic element R in lithium position and iron position, any one metallic element or any two metallic elements of displacement metallic element R for selecting from the group being formed by aluminium, nickel, titanium and magnesium, and, 0.06≤x≤0.15,0.06≤y≤0.15;
Wherein, metallic compound is one or both that select in the group being comprised of ferric nitrate, nickel nitrate, cobalt nitrate, sodium nitrate, potassium nitrate, ferric acetate, nickel acetate, cobalt acetate, sodium sulphate, potassium sulfate, sodium carbonate, potash, sodium chloride and potassium chloride;
Wherein, conductive auxiliary agent is one or both that select in the group being comprised of acetylene black, electrically conductive graphite, conductive carbon black, sucrose and glucose.
3. iron phosphate lithium electrode material as claimed in claim 2, is characterized in that:
Li 1-xr x+yfe 1-ypO 4be preferably 100 parts, metallic compound is preferably 20 parts, and conductive auxiliary agent is preferably 10 parts.
CN201310501218.0A 2013-10-22 2013-10-22 Lithium iron phosphate electrode material Pending CN103594678A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101339994A (en) * 2008-09-01 2009-01-07 罗绍华 Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof
CN101964413A (en) * 2010-10-13 2011-02-02 临沂杰能新能源材料有限公司 Nanoscale lithium iron phosphate electrode material and preparation method thereof
CN101997118A (en) * 2010-11-02 2011-03-30 天津斯特兰能源科技有限公司 Lithium ferric manganese phosphate as cathode material of lithium ion battery and preparation method thereof
JP5153994B2 (en) * 2003-12-18 2013-02-27 コミサリア ア レネルジー アトミック エ オ ゼネルジー アルテルナティブ Lithium storage battery exhibiting both high potential and high lithium insertion capacity
CN103066280A (en) * 2012-12-28 2013-04-24 珠海泰坦能源电子技术有限公司 Spherical lithium iron phosphate anode material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5153994B2 (en) * 2003-12-18 2013-02-27 コミサリア ア レネルジー アトミック エ オ ゼネルジー アルテルナティブ Lithium storage battery exhibiting both high potential and high lithium insertion capacity
CN101339994A (en) * 2008-09-01 2009-01-07 罗绍华 Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof
CN101964413A (en) * 2010-10-13 2011-02-02 临沂杰能新能源材料有限公司 Nanoscale lithium iron phosphate electrode material and preparation method thereof
CN101997118A (en) * 2010-11-02 2011-03-30 天津斯特兰能源科技有限公司 Lithium ferric manganese phosphate as cathode material of lithium ion battery and preparation method thereof
CN103066280A (en) * 2012-12-28 2013-04-24 珠海泰坦能源电子技术有限公司 Spherical lithium iron phosphate anode material and preparation method thereof

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Application publication date: 20140219