CN103794757B - A kind of preparation method of lithium manganese phosphate-carbon composite - Google Patents

A kind of preparation method of lithium manganese phosphate-carbon composite Download PDF

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CN103794757B
CN103794757B CN201410059103.5A CN201410059103A CN103794757B CN 103794757 B CN103794757 B CN 103794757B CN 201410059103 A CN201410059103 A CN 201410059103A CN 103794757 B CN103794757 B CN 103794757B
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lithium
manganese phosphate
lithium manganese
potassium
carbon composite
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CN103794757A (en
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李鹏
梁玉蓉
朱开金
赵彦亮
谭俊华
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Taiyuan Institute of Technology
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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
    • H01M4/62—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
    • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The preparation method that the present invention relates to a kind of lithium manganese phosphate-carbon composite, the method comprises the steps: (1) this potassium, the chemical formula of nickel doping phosphoric acid manganese lithium is Li1-xKxMn1-yNiyPO4, wherein: x=0.05-0.1, y=0.1-0.15, weigh lithium oxalate, potassium chloride, manganese nitrate, diammonium phosphate and nickel sulfate according to the mole of Li, K, Mn, Ni, P in above-mentioned chemical formula, be dissolved in deionized water after mixing, form mixed solution; Under an argon atmosphere, add that hydrazine hydrate reduction agent is continuously stirred obtains mixture; The mixture obtained is carried out spray drying, obtains the lithium manganese phosphate presoma of the potassium of spherical solid, nickel doping; (2) after being mixed by the lithium manganese phosphate presoma of acetylene black and above-mentioned potassium, nickel doping, carrying out ball milling under an argon atmosphere, sintering obtains lithium manganese phosphate-carbon composite. Lithium manganese phosphate-carbon composite prepared by the present invention, adulterated by lithium manganese phosphate composite K, Ni are modified to improve its Ionic diffusion energy, to improve its activity.

Description

A kind of preparation method of lithium manganese phosphate-carbon composite
Art
The preparation method that the present invention relates to a kind of lithium manganese phosphate-carbon composite.
Background technology
Lithium ion battery is prepared by one or more lithium electrochemical ponds, and described lithium electrochemical pond includes negative pole (anode), positive pole (negative electrode) and is used for promoting ionic charge carrier electrolyte of movement between negative pole and positive pole. Electrode uses Insertion compound two kinds different: a kind of for activated cathode, a kind of for anode material.
Have been able to make light-duty based on the high-energy-density of reversible some material of embedding of lithium and long-life rechargeable battery and compact electronic device is widely distributed, described electronic installation such as mobile phone and portable computer. But, some anode material, such as LiCoO2Application caused worry, reason is in that the toxicity of cobalt, due to the oxygen fire that causes of release and blast danger and overcharge or when the temperature raised with the vigorous reaction (thermal runaway) of organic bath. And, cobalt is quite rare and be therefore expensive element. Other material, such as LiMn2O4There are poor long-time stability.
Oxonium ion in olivine structural and P5+And PO4 3-Tetrahedron polyanionic forms strong covalent bond with stable three-dimension-framework. Other lithium transition-metal oxide such as LiCoO2��LiNiO2��LiMnO2And LiMn2O4Lock into significant capacity decline in cyclic process. This is owing to extracting and being inserted into the structural rearrangement caused in process. LiMnPO4There is provided relative to Li+The redox potential of the 4.1V of/Li, this is considered as the major part obtainable maximum limit of liquid electrolyte. But LiMnPO4Also there is during as positive electrode inevitable shortcoming. First, LiMnPO4Room temperature electron electrical conductivity low, this can pass through at LiMnPO4Particle surface coated with conductive material (such as carbon) or ion doping improve; Secondly, Li+At LiMnPO4In diffusion admittance be one-dimensional, thus diffusion velocity is slow so that the high rate during charging-discharging of material is poor, and the utilization rate of active substance is on the low side.
Summary of the invention
The preparation method that the present invention provides a kind of lithium manganese phosphate-carbon composite, the positive electrode using the method to prepare, there is excellent conductive performance and high specific capacity.
To achieve these goals, the preparation method of a kind of lithium manganese phosphate-carbon composite provided by the invention, the method comprises the steps:
(1) the lithium manganese phosphate presoma of potassium, nickel doping is prepared
This potassium, nickel doping phosphoric acid manganese lithium chemical formula be Li1-xKxMn1-yNiyPO4Wherein: x=0.05-0.1, y=0.1-0.15, lithium oxalate, potassium chloride, manganese nitrate, diammonium phosphate and nickel sulfate are weighed according to the mole of Li, K, Mn, Ni, P in above-mentioned chemical formula, it is dissolved in after mixing in deionized water, forms the mixed solution that lithium concentration is 0.1-0.3mol/L;
Under an argon atmosphere, at 60-80 DEG C, add and enough make Mn3+It is reduced into Mn2+The continuously stirred 8-10h of hydrazine hydrate reduction agent, obtain mixture;
The mixture obtained is carried out spray drying, specific as follows: the mixture of acquisition carries out through narrow nozzle, wherein obtain small droplet, they are by hot-air dry, hot-air has the temperature of 120-130 DEG C, and spray drying obtains the lithium manganese phosphate presoma of the potassium of spherical solid, nickel doping;
(2) carbon cladding
To have specific surface area is 100-150m2After the lithium manganese phosphate presoma of the acetylene black of the conduction of/g and above-mentioned potassium, nickel doping mixes according to mass ratio 3-5:100, carry out ball milling under an argon atmosphere, grinding rate is 400-500r/min, Ball-milling Time is 8-10h, after ball milling terminates, at 700-750 DEG C, sinter 6-8h namely obtain lithium manganese phosphate-carbon composite.
Lithium manganese phosphate-carbon composite prepared by the present invention, adulterated by lithium manganese phosphate composite K, Ni are modified to improve its Ionic diffusion energy, to improve its activity, and at one layer of carbon of its Surface coating so that it has good electric conductivity and cyclical stability. Therefore this composite is when for lithium ion battery, has higher specific capacity and longer service life.
Detailed description of the invention
Embodiment one
Prepare the lithium manganese phosphate presoma of potassium, nickel doping
Potassium, nickel doping phosphoric acid manganese lithium chemical formula be Li0.95K0.05Mn0.9Ni0.1PO4, weigh lithium oxalate, potassium chloride, manganese nitrate, diammonium phosphate and nickel sulfate according to the mole of Li, K, Mn, Ni, P in above-mentioned chemical formula, be dissolved in deionized water after mixing, form the mixed solution that lithium concentration is 0.1mol/L.
Under an argon atmosphere, at 60 DEG C, add and enough make Mn3+It is reduced into Mn2+The continuously stirred 10h of hydrazine hydrate reduction agent, obtain mixture.
The mixture obtained is carried out spray drying, specific as follows: the mixture of acquisition carries out through narrow nozzle, wherein obtain small droplet, they are by hot-air dry, hot-air has the temperature of 120 DEG C, and spray drying obtains the lithium manganese phosphate presoma of the potassium of spherical solid, nickel doping.
Carbon is coated with
To have specific surface area is 100-150m2After the lithium manganese phosphate presoma of the acetylene black of the conduction of/g and above-mentioned potassium, nickel doping mixes according to mass ratio 3:100, carrying out ball milling under an argon atmosphere, grinding rate is 400r/min, and Ball-milling Time is 8h, after ball milling terminates, at 700 DEG C, sinter 8h namely obtain lithium manganese phosphate-carbon composite.
Embodiment two
Prepare the lithium manganese phosphate presoma of potassium, nickel doping
Potassium, nickel doping phosphoric acid manganese lithium chemical formula be Li0.9K0.1Mn0.85Ni0.15PO4, weigh lithium oxalate, potassium chloride, manganese nitrate, diammonium phosphate and nickel sulfate according to the mole of Li, K, Mn, Ni, P in above-mentioned chemical formula, be dissolved in deionized water after mixing, form the mixed solution that lithium concentration is 0.3mol/L.
Under an argon atmosphere, at 80 DEG C, add and enough make Mn3+It is reduced into Mn2+The continuously stirred 8h of hydrazine hydrate reduction agent, obtain mixture.
The mixture obtained is carried out spray drying, specific as follows: the mixture of acquisition carries out through narrow nozzle, wherein obtain small droplet, they are by hot-air dry, hot-air has the temperature of 130 DEG C, and spray drying obtains the lithium manganese phosphate presoma of the potassium of spherical solid, nickel doping.
Carbon is coated with
To have specific surface area is 100-150m2After the lithium manganese phosphate presoma of the acetylene black of the conduction of/g and above-mentioned potassium, nickel doping mixes according to mass ratio 5:100, carrying out ball milling under an argon atmosphere, grinding rate is 500r/min, and Ball-milling Time is 8h, after ball milling terminates, at 750 DEG C, sinter 6h namely obtain lithium manganese phosphate-carbon composite.
Comparative example
The manganese nitrate of 0.4mol/L and 0.2mol/L sodium radio-phosphate,P-32 solution equal-volume are mixed (mol ratio Mn: P=2: 1), stirring, regulating pH with the salpeter solution of 1mol/L is that 4 (nitric acid also makes oxidant, making bivalent manganese be oxidized to manganic, the amount regulating the nitric acid used by pH value ensure that oxidant is excessive), stirring reaction is after 3 hours, sucking filtration, successively by deionized water and washing with alcohol, dry, obtain the manganese phosphate (MnPO of activity4), described manganese phosphate weighs activity manganese phosphate and lithium carbonate with water of crystallization according to mol ratio Li: Mn=1.05, mixing, and add sucrose, sucrose addition is the 15% of activity manganese phosphate and lithium carbonate gross mass, above-mentioned substance is carried out ball milling, using ethanol as disperse medium, after the rotating speed ball milling 10 hours of 350rpm, carry out spray drying, dried powder carries out heat treatment in High Purity Nitrogen air-flow, it is warming up to 400 DEG C with the heating rate of 5 DEG C/min, calcine 6 hours, in heat treated process, manganic is reduced into bivalent manganese, then natural cooling, obtain manganese phosphate lithium/carbon composite material, the distribution of its grain diameter is 100��500nm.
Above-described embodiment one, two and comparative example products therefrom are mixed with the ratio of mass ratio 80: 10: 10 with conductive black and binding agent Kynoar, is fabricated to the test battery of same specification. Reference electrode is lithium metal, and electrolyte is 1mol/lLiPF6EC/DEC/DMC (volume ratio 1: 1: 1). Test temperature be at 25 DEG C, carry out electric performance test, after tested this embodiment one with two material compared with the product of comparative example, first charge-discharge capacity improves 27-34%, brings up to more than 1.5 times service life.

Claims (1)

1. a preparation method for lithium manganese phosphate-carbon composite, the method comprises the steps:
(1) the lithium manganese phosphate presoma of potassium, nickel doping is prepared
This potassium, nickel doping phosphoric acid manganese lithium chemical formula be Li1-xKxMn1-yNiyPO4Wherein: x=0.05-0.1, y=0.1-0.15, lithium oxalate, potassium chloride, manganese nitrate, diammonium phosphate and nickel sulfate is weighed according to the mole of Li, K, Mn, Ni, P in above-mentioned chemical formula, it is dissolved in after mixing in deionized water, forms the mixed solution that lithium concentration is 0.1-0.3mol/L;
Under an argon atmosphere, at 60-80 DEG C, add and make Mn3+It is reduced into Mn2+The continuously stirred 8-10h of hydrazine hydrate reduction agent, obtain mixture;
The mixture obtained is carried out spray drying, specific as follows: the mixture of acquisition carries out through narrow nozzle, wherein obtain small droplet, they are by hot-air dry, hot-air has the temperature of 120-130 DEG C, and spray drying obtains the lithium manganese phosphate presoma of the potassium of spherical solid, nickel doping;
(2) carbon cladding
To have specific surface area is 100-150m2After the lithium manganese phosphate presoma of the acetylene black of the conduction of/g and above-mentioned potassium, nickel doping mixes according to mass ratio 3-5:100, carry out ball milling under an argon atmosphere, grinding rate is 400-500r/min, Ball-milling Time is 8-10h, after ball milling terminates, at 700-750 DEG C, sinter 6-8h namely obtain lithium manganese phosphate-carbon composite.
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CN102646828A (en) * 2012-04-19 2012-08-22 中南大学 Method for preparing anode material LiMnPO4/C of lithium ion battery
CN103346295A (en) * 2013-07-11 2013-10-09 苏州懿源宏达知识产权代理有限公司 Preparation method of multi-element doped lithium iron phosphate composite positive pole material

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KR100701248B1 (en) * 2004-11-16 2007-04-06 한국전기연구원 Carbon-coated lithium transition metal phosphates for active cathode material for lithium secondary battery and manufacturing method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102646828A (en) * 2012-04-19 2012-08-22 中南大学 Method for preparing anode material LiMnPO4/C of lithium ion battery
CN103346295A (en) * 2013-07-11 2013-10-09 苏州懿源宏达知识产权代理有限公司 Preparation method of multi-element doped lithium iron phosphate composite positive pole material

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