CN107834026A - The combination electrode material and its preparation technology of a kind of high conductivity - Google Patents
The combination electrode material and its preparation technology of a kind of high conductivity Download PDFInfo
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- CN107834026A CN107834026A CN201710553884.7A CN201710553884A CN107834026A CN 107834026 A CN107834026 A CN 107834026A CN 201710553884 A CN201710553884 A CN 201710553884A CN 107834026 A CN107834026 A CN 107834026A
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- electrode material
- combination electrode
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/36—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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- 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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- General Chemical & Material Sciences (AREA)
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- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of combination electrode material of high conductivity and its preparation technology.The material is with FeC2O4・2H2O、LiOH、NH4H2PO4, Nd powder and Mn powder as raw material, first by Li1‑ xNdxFe1‑yMnyPO4Atom ratio prepare the mixture of certain mass, then carry out mechanical ball mill by ball-milling technology, carry out high temperature sintering after ball milling, sintered powder can obtain combination electrode material micro mist.The combination electrode material micro mist of preparation has the advantages that high conductivity and technique is simple, flow is short.
Description
Technical field
The present invention relates to a kind of li-ion electrode materials and its preparation technology, more particularly to a kind of height for adding manganese element is led
Electric rate li-ion electrode materials and preparation method thereof, belong to electrode material field.
Background technology
With getting worses such as shortage of resources, oil crisises, the mankind are increasingly compeled using cleaning, other efficient energy
Cut, oil is replaced with electricity, reduce municipal pollution, development electric car is the task of top priority.Lithium ion battery is with monomer operating voltage
Height, high-energy-density density, have extended cycle life, self-discharge rate is small, memory-less effect, it is green the advantages that.Positive electrode uses
Exploitation to lithium battery is particularly critical, and anode material for lithium-ion batteries common at present mainly has the cobalt acid lithium and olive of layer structure
LiFePO4 of olive stone structure etc..Wherein, LiCoO2Structure is more stable, electrochemical performance, is the current ratio of commercialization
More ripe positive electrode, but the overcharge resistant ability of this material is poor, declines rapidly in higher charging voltage specific capacity；
LiFePO4Belong to newer positive electrode, its is safe, cost is relatively low, is outstanding positive electrode.LiFePO4With somewhat
The hexagonal closs packing arrangement architecture of distortion, belong to rhombic system, space group Pnma.In the a-c planes where lithium atom
In, include PO4Tetrahedron, which limits the mobile space of lithium ion, therefore its Conductivity Ratio others stratiform chemical combination
Thing is low.The shortcomings that due to LiFePO 4 material itself, lithium ion is relatively low in LiFePO 4 material particle diffusion inside speed, and material
The electron conduction of material is also poor.
The content of the invention
The present invention prepares a kind of composite lithium ion cell composite positive pole by high temperature solid-state method reaction.Rare earth Nd has
Preferable electromagnetic performance, Li position can be instead of, is dissolved into well in olivine structural, improve LiFePO4Conduction
Rate.Doping manganese ion can improve LiFePO4Heavy-current discharge performance, make up LiFePO4Deficiency.A kind of composite lithium ion cell
Composite positive pole, make up LiFePO4Deficiency, improve LiFePO4Conduction and charge-discharge performance.Specific preparation technology includes
Following steps：
(1) the pure FeC of appropriate chemistry is taken2O4・2H2O、LiOH、NH4H2PO4, Nd powder and Mn powder as raw material, according to Li1- xNdxFe1-yMnyPO4（0.01≤x≤0.1, 0. 1≤y≤0.2）Atom ratio prepare raw material；
(2) the raw material prepared is carried out carrying out ball milling after tentatively mixing；
(3) under the protection of nitrogen, the mixture of ball milling is raised into temperature to 300 DEG C, constant temperature 5-10 hours；
(4) continue said mixture raising temperature to 600 DEG C, then constant temperature 10-20 hours；
(5) furnace cooling after the completion of reacting, collect powder and produce product.
Preferentially, described step (1) in, according to Li0.97Nd0.03Fe0.85Mn0.15PO4Atomic ratio dispensing.
Preferentially, described step (2) in, protected in mechanical milling process with argon gas.
Preferentially, described step (2) in, ball milling speed set 200-400 revs/min, Ball-milling Time is 8-10 hours.
Preferentially, described step (3) in, the control of 300 DEG C of constant temperature times is in 6-8 hours.
Preferentially, described step (4) in, the control of 600 DEG C of constant temperature times is in 15-20 hours.
The present invention has following advantages and characteristic：
(1) the electrode material conductance prepared is high, and charge-discharge performance is good；
(2) preparation technology is simple, and flow is short.
Embodiment one：
With the pure FeC of chemistry2O4・2H2O、LiOH、NH4H2PO4, Nd powder and Mn powder as raw material, according to
Li0.97Nd0.03Fe0.85Mn0.15PO4Atom ratio dispensing, be made into 5g mixture, the mixture material prepared carried out preliminary
Poured into together in ball grinder after mixing, then toward the appropriate grinding steel ball of addition in ball grinder, then cover ball grinder lid and tighten
Screw, then vacuum pumping is carried out with air exhauster, it is evacuated to air pressure in tank and is stopped operation after being less than 0.1 atmospheric pressure, it is then past again
Ball grinder is filled with appropriate argon gas as protective gas, then puts it into and ball milling is carried out in planetary ball mill, the speed of rotational speed of ball-mill
Degree is arranged to 200 revs/min, after ball milling 8h, removes after ball grinder stands a period of time, releases in ball grinder after gas decompression,
Ball grinder is opened, alloy powder in ball grinder is taken out, is put into a container, is heated at high temperature under the protective condition of nitrogen
To 300 DEG C, constant temperature 6 hours, temperature is then raised to 600 DEG C, constant temperature 15 hours, last furnace cooling, powder is collected and produces production
Product.
Embodiment two：
With the pure FeC of chemistry2O4・2H2O、LiOH、NH4H2PO4, Nd powder and Mn powder as raw material, according to
Li0.99Nd0.01Fe0.9Mn0.1PO4Atom ratio dispensing, be made into 20g mixture, the mixture material prepared carried out preliminary
Poured into together in ball grinder after mixing, then toward the appropriate grinding steel ball of addition in ball grinder, then cover ball grinder lid and tighten
Screw, then vacuum pumping is carried out with air exhauster, it is evacuated to air pressure in tank and is stopped operation after being less than 0.1 atmospheric pressure, it is then past again
Ball grinder is filled with appropriate argon gas as protective gas, then puts it into and ball milling is carried out in planetary ball mill, the speed of rotational speed of ball-mill
Degree is arranged to 300 revs/min, after ball milling 9h, removes after ball grinder stands a period of time, releases in ball grinder after gas decompression,
Ball grinder is opened, alloy powder in ball grinder is taken out, is put into a container, is heated at high temperature under the protective condition of nitrogen
To 300 DEG C, constant temperature 7 hours, temperature is then raised to 600 DEG C, constant temperature 18 hours, last furnace cooling, powder is collected and produces production
Product.
Embodiment three：
With the pure FeC of chemistry2O4・2H2O、LiOH、NH4H2PO4, Nd powder and Mn powder as raw material, according to
Li0.9Nd0.1Fe0.8Mn0.2PO4Atom ratio dispensing, be made into 50g mixture, the mixture material prepared carried out preliminary
Poured into together in ball grinder after mixing, then toward the appropriate grinding steel ball of addition in ball grinder, then cover ball grinder lid and tighten
Screw, then vacuum pumping is carried out with air exhauster, it is evacuated to air pressure in tank and is stopped operation after being less than 0.1 atmospheric pressure, it is then past again
Ball grinder is filled with appropriate argon gas as protective gas, then puts it into and ball milling is carried out in planetary ball mill, the speed of rotational speed of ball-mill
Degree is arranged to 400 revs/min, after ball milling 10h, removes after ball grinder stands a period of time, releases in ball grinder after gas decompression,
Ball grinder is opened, alloy powder in ball grinder is taken out, then powder is fitted into the quartz glass tube of an end closure, is full of inside
Appropriate nitrogen, then make its sealing with the thermal-flame vitreous silica tube opening other end, by the quartz glass tube input water of sealing
Air-tightness is verified, if bubble-free, can assert that its sealing is good, then be carried out being heated at high temperature to 300 DEG C, constant temperature 8 is small
When, temperature is then raised to 600 DEG C, constant temperature 20 hours, last furnace cooling, is collected powder and is produced product.
Claims (6)
1. a kind of combination electrode material of high conductivity, it is characterised in that the preparation technology of the material is carried out as follows：
(1) the pure FeC of appropriate chemistry is taken2O4・2H2O、LiOH、NH4H2PO4, Nd powder and Mn powder as raw material, according to Li1-xNdxFe1- yMnyPO4（0.01≤x≤0.1, 0. 1≤y≤0.2）Atom ratio prepare raw material；
(2) the raw material prepared is carried out carrying out ball milling after tentatively mixing；
(3) under the protection of nitrogen, the mixture of ball milling is raised into temperature to 300 DEG C, constant temperature 5-10 hours；
(4) continue said mixture raising temperature to 600 DEG C, then constant temperature 10-20 hours；
(5) furnace cooling after the completion of reacting, collect powder and produce product.
A kind of 2. combination electrode material of high conductivity as claimed in claim 1, it is characterised in that step (1) in, atom is matched somebody with somebody
Than according to Li0.97Nd0.03Fe0.85Mn0.15PO4Atomic ratio dispensing.
A kind of 3. combination electrode material of high conductivity as described in claim 1 or 2, it is characterised in that step (2) in, ball
Protected during mill with argon gas.
A kind of 4. combination electrode material of high conductivity as described in claim 1 or 2, it is characterised in that step (2) in, ball
Grind speed and set 200-400 revs/min, Ball-milling Time is 8-10 hours.
A kind of 5. combination electrode material of high conductivity as described in claim 1 or 2, it is characterised in that described step
(3) in, 300 DEG C of constant temperature time controls are in 6-8 hours.
A kind of 6. combination electrode material of high conductivity as described in claim 1 or 2, it is characterised in that described step
(4) in, 600 DEG C of constant temperature time controls are in 15-20 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710553884.7A CN107834026A (en) | 2017-07-09 | 2017-07-09 | The combination electrode material and its preparation technology of a kind of high conductivity |
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| CN201710553884.7A CN107834026A (en) | 2017-07-09 | 2017-07-09 | The combination electrode material and its preparation technology of a kind of high conductivity |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785800A (en) * | 2005-12-23 | 2006-06-14 | 清华大学 | Preparation method of rare earth doped iron lithium phosphate powder |
| CN1830764A (en) * | 2006-04-03 | 2006-09-13 | 清华大学 | Rare earth doped carbon clad type nanometer anode material iron lithium phosphate and its preparation method |
| 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 |
| CN105514430A (en) * | 2015-12-30 | 2016-04-20 | 山东精工电子科技有限公司 | Spherical LiFexMnyPO4 anode material and preparation method thereof |
-
2017
- 2017-07-09 CN CN201710553884.7A patent/CN107834026A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785800A (en) * | 2005-12-23 | 2006-06-14 | 清华大学 | Preparation method of rare earth doped iron lithium phosphate powder |
| CN1830764A (en) * | 2006-04-03 | 2006-09-13 | 清华大学 | Rare earth doped carbon clad type nanometer anode material iron lithium phosphate and its preparation method |
| 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 |
| CN105514430A (en) * | 2015-12-30 | 2016-04-20 | 山东精工电子科技有限公司 | Spherical LiFexMnyPO4 anode material and preparation method thereof |
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Application publication date: 20180323 |