CN107834025A - A kind of compound lithium ion electrode material - Google Patents
A kind of compound lithium ion electrode material Download PDFInfo
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- CN107834025A CN107834025A CN201710553659.3A CN201710553659A CN107834025A CN 107834025 A CN107834025 A CN 107834025A CN 201710553659 A CN201710553659 A CN 201710553659A CN 107834025 A CN107834025 A CN 107834025A
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- Prior art keywords
- lithium ion
- electrode material
- ion electrode
- compound lithium
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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
-
- 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
-
- 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 kind of compound lithium ion electrode material.The preparation method of the electrode material is：With FeC2O4・2H2O、Li2CO3、NH4H2PO4, Mn powder and Ce powder as raw material, according to Li1‑xCex Fe1‑yMnyPO4Atom ratio prepare raw material and to be mixed, then carry out ball milling, mixture first constant temperature more than 5 hours under 300 DEG C of environment, then constant temperature more than 10 hours under 600 DEG C of environment after ball milling, after it is reacted high temperature sintering, natural cooling, collect powder and produce product.
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 addition rare earth and manganese element
Positive electrode and preparation method thereof, belong to battery electrode material field.
Background technology
Anode material for lithium-ion batteries common at present mainly has the phosphoric acid of the cobalt acid lithium and olivine structural of layer structure
Iron lithium etc..Wherein LiCoO2Structure is more stable, electrochemical performance, is the positive pole material of current commercialization comparative maturity
Material, but the overcharge resistant ability of this material is poor, declines rapidly in higher charging voltage specific capacity；LiFePO4Belong to compared with
New positive electrode, its is safe, cost is relatively low, is outstanding positive electrode.But it is low room-temperature conductivity to be present, its high current
Charge-discharge performance need further to improve, and therefore, develops composite positive pole grinding into anode material for lithium-ion batteries
Study carefully one of direction.
LiFePO4With the hexagonal closs packing arrangement architecture somewhat distorted, belong to rhombic system, space group Pnma.
In a-c planes where lithium atom, include PO4Tetrahedron, which limits the mobile space of lithium ion, therefore it
Conductivity Ratio others lamellar compound is low.Rare earth element is metal material " vitamin ", the performance to improving metal material
There play the role of to be special.There is document to point out, rare earth element ce can instead of Li position, be dissolved into olivine structural well
In, and LiFePO can be improved4Conductance；Doping manganese ion can improve LiFePO4Heavy-current discharge performance.The present invention passes through
Ball-milling technology and high temperature solid-state method reaction prepare a kind of composite lithium ion cell composite positive pole, and the material of preparation makes up
LiFePO4Deficiency, improve LiFePO4Conduction and charge-discharge performance.
The content of the invention
It is an object of the invention to provide a kind of composite lithium ion cell composite positive pole and its preparation technology.The preparation work
Skill comprises the following steps：
(1) the pure FeC of appropriate chemistry is taken2O4・2H2O 、Li2CO3、NH4H2PO4, metal Mn powder and metal Ce powder be as former
Material, according to Li1-xCe x Fe1-y MnyPO4（0.01≤x≤0.1, 0. 1≤y≤0.3）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 more than 5 hours；
(4) continue said mixture raising temperature to 650 DEG C, then constant temperature more than 12 hours；
(5) furnace cooling after the completion of reacting, collect powder and produce product.
Preferentially, step (1) in, according to Li0.97Ce0.03Fe0.85Mn0.15PO4Atomic ratio dispensing.
Preferentially, step (2) in, protected in mechanical milling process with argon gas.
Preferentially, step (2) in, ball milling speed set 200-300 revs/min.
Preferentially, step (2) in, Ball-milling Time is 10-12 hours.
Preferentially, step (3) in, the control of 300 DEG C of constant temperature times is in 6-7 hours.
Preferentially, step (4) in, the control of 650 DEG C of constant temperature times is in 21-23 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；
(3) condition control is simple, it is easy to accomplish industrialization.
Embodiment one：
With the pure FeC of chemistry2O4・2H2O 、Li2CO3、NH4H2PO4, metal Mn powder and metal Ce powder as raw material, according to
Li0.97Ce0.03Fe0.85Mn0.15PO4Atom ratio dispensing 5g mixture, the mixture material prepared is tentatively mixed
Pour into together in ball grinder afterwards, then steel ball ground toward addition in ball grinder is appropriate, then cover ball grinder lid and tighten screw,
Vacuum pumping is carried out with air exhauster again, air pressure in tank is evacuated to and is stopped operation after being less than 0.1 atmospheric pressure, then again toward ball grinder
Appropriate argon gas is filled with 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 is set
For 200 revs/min, after ball milling 12h, remove after ball grinder stands a period of time, release in ball grinder after gas decompression, open ball
Grinding jar, alloy powder in ball grinder is taken out, be put into a container, carry out being heated at high temperature to 300 under the protective condition of nitrogen
DEG C, constant temperature 6 hours, temperature is then raised to 650 DEG C, constant temperature 21 hours, last furnace cooling, powder is collected and produces product.
Embodiment two：
With the pure FeC of chemistry2O4・2H2O 、Li2CO3、NH4H2PO4, metal Mn powder and metal Ce powder as raw material, according to
Li0.99Ce0.01Fe0.9Mn0.1PO4Atom ratio dispensing 20g mixture, the mixture material prepared is tentatively mixed
Pour into together in ball grinder afterwards, then steel ball ground toward addition in ball grinder is appropriate, then cover ball grinder lid and tighten screw,
Vacuum pumping is carried out with air exhauster again, air pressure in tank is evacuated to and is stopped operation after being less than 0.1 atmospheric pressure, then again toward ball grinder
Appropriate argon gas is filled with 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 is set
For 250 revs/min, after ball milling 11h, remove after ball grinder stands a period of time, release in ball grinder after gas decompression, open ball
Grinding jar, alloy powder in ball grinder is taken out, be put into a container, carry out being heated at high temperature to 300 under the protective condition of nitrogen
DEG C, constant temperature 6 hours, temperature is then raised to 650 DEG C, constant temperature 22 hours, last furnace cooling, powder is collected and produces product.
Embodiment three：
With the pure FeC of chemistry2O4・2H2O 、Li2CO3、NH4H2PO4, metal Mn powder and metal Ce powder as raw material, according to
Li0.9Ce0.1Fe0.7Mn0.3PO4Atom ratio dispensing 50g mixture, by the mixture material prepared carry out tentatively mix after
Pour into together in ball grinder, then steel ball is ground toward addition in ball grinder is appropriate, then cover ball grinder lid and tighten screw, then
Vacuum pumping is carried out with air exhauster, air pressure in tank is evacuated to and is stopped operation after being less than 0.1 atmospheric pressure, then filled again toward ball grinder
Enter appropriate argon gas as protective gas, then put it into and ball milling is carried out in planetary ball mill, the speed of rotational speed of ball-mill is arranged to
300 revs/min, after ball milling 10h, remove after ball grinder stands a period of time, release in ball grinder after gas decompression, open ball milling
Tank, alloy powder in ball grinder is taken out, then powder is fitted into the quartz glass tube of an end closure, inside full of appropriate nitrogen
Gas, then make its sealing with the thermal-flame vitreous silica tube opening other end, gas will be verified in the quartz glass tube input water of sealing
It close property, 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 7 hours, then
Temperature is raised to 650 DEG C, constant temperature 23 hours, last furnace cooling, powder is collected and produces product.
Claims (7)
1. a kind of compound lithium ion electrode material, it is characterised in that the preparation method of the electrode material is carried out as follows：
(1) the pure FeC of appropriate chemistry is taken2O4・2H2O 、Li2CO3、NH4H2PO4, metal Mn powder and metal Ce powder as raw material,
According to Li1-xCe x Fe1-y MnyPO4（0.01≤x≤0.1, 0. 1≤y≤0.3）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 more than 5 hours；
(4) continue said mixture raising temperature to 650 DEG C, then constant temperature more than 12 hours；
(5) furnace cooling after the completion of reacting, collect powder and produce product.
2. a kind of compound lithium ion electrode material as claimed in claim 1, it is characterised in that prepared by material the step of (1)
In, according to Li0.97Ce0.03Fe0.85Mn0.15PO4Atomic ratio dispensing.
3. a kind of compound lithium ion electrode material as described in claim 1 or 2, it is characterised in that in step prepared by material
Suddenly (2) in, protected in mechanical milling process with argon gas.
4. a kind of compound lithium ion electrode material as described in claim 1 or 2, it is characterised in that in step prepared by material
Suddenly (2) in, ball milling speed set 200-300 revs/min.
5. a kind of compound lithium ion electrode material as described in claim 1 or 2, it is characterised in that in step prepared by material
Suddenly (2) in, Ball-milling Time is 10-12 hours.
6. a kind of compound lithium ion electrode material as described in claim 1 or 2, it is characterised in that in step prepared by material
Suddenly (3) in, the control of 300 DEG C of constant temperature times is in 6-7 hours.
7. a kind of compound lithium ion electrode material as described in claim 1 or 2, it is characterised in that in step prepared by material
Suddenly (4) in, the control of 650 DEG C of constant temperature times is in 21-23 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710553659.3A CN107834025A (en) | 2017-07-08 | 2017-07-08 | A kind of compound lithium ion electrode material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710553659.3A CN107834025A (en) | 2017-07-08 | 2017-07-08 | A kind of compound lithium ion electrode material |
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| CN107834025A true CN107834025A (en) | 2018-03-23 |
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| CN201710553659.3A Withdrawn CN107834025A (en) | 2017-07-08 | 2017-07-08 | A kind of compound lithium ion electrode material |
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Citations (6)
| 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 |
| WO2009127901A1 (en) * | 2008-04-14 | 2009-10-22 | High Power Lithium S.A. | Lithium metal phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
| CN104347875A (en) * | 2014-09-28 | 2015-02-11 | 山东精工电子科技有限公司 | Positive electrode material lithium iron manganese phosphate of lithium-ion battery and a preparing method of positive electrode material |
| CN105428651A (en) * | 2015-12-23 | 2016-03-23 | 郑春燕 | Rare-earth cerium-doped lithium iron phosphate composite electrode material |
| CN105428652A (en) * | 2015-12-23 | 2016-03-23 | 郑春燕 | Novel rare-earth-lithium iron phosphate composite electrode material 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
- 2017-07-08 CN CN201710553659.3A patent/CN107834025A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009127901A1 (en) * | 2008-04-14 | 2009-10-22 | High Power Lithium S.A. | Lithium metal phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
| 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 |
| CN104347875A (en) * | 2014-09-28 | 2015-02-11 | 山东精工电子科技有限公司 | Positive electrode material lithium iron manganese phosphate of lithium-ion battery and a preparing method of positive electrode material |
| CN105428651A (en) * | 2015-12-23 | 2016-03-23 | 郑春燕 | Rare-earth cerium-doped lithium iron phosphate composite electrode material |
| CN105428652A (en) * | 2015-12-23 | 2016-03-23 | 郑春燕 | Novel rare-earth-lithium iron phosphate composite electrode material 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 |