CN107834059A - A kind of preparation technology of novel composite electrode material - Google Patents
A kind of preparation technology of novel composite electrode material Download PDFInfo
- Publication number
- CN107834059A CN107834059A CN201710553784.4A CN201710553784A CN107834059A CN 107834059 A CN107834059 A CN 107834059A CN 201710553784 A CN201710553784 A CN 201710553784A CN 107834059 A CN107834059 A CN 107834059A
- Authority
- CN
- China
- Prior art keywords
- preparation technology
- electrode material
- powder
- hours
- ball milling
- 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.)
- Withdrawn
Links
Classifications
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation technology of novel composite electrode material.The technique is with FeC2O4・2H2O、Li2CO3、NH4H2PO4, a kind of LiFePO4 combination electrode material for being prepared as raw material of metal Mn powder and rare earth Pr powder.First according to Li1‑x La x Fe1‑y MnyPO4Atom ratio dispensing, be put into after preliminary mixing in ball grinder and ball milling carried out under the protective condition of argon gas, segmented high-temperature sintering is carried out after ball milling, cooling collects powder and produces product.The present invention has the advantages that preparation technology is simple, flow is short, and the electrode material performance of preparation is good.
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 element and manganese
Li-ion electrode materials of element 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.There is document to point out, rare earth element can instead of Li position, be dissolved into well
In olivine structural, and LiFePO can be improved4Conductance, and rare earth Pr has preferable electromagnetic performance, is entrained in
LiFePO4In structure, its performance can be improved.Doping manganese ion can improve LiFePO4Heavy-current discharge performance.The present invention passes through
High temperature solid-state method reaction prepares a kind of composite lithium ion cell composite positive pole, makes up LiFePO4Deficiency, improve LiFePO4
Conduction and charge-discharge performance.
The content of the invention
It is an object of the invention to provide a kind of compound lithium ion electrode material and its preparation technology.The preparation technology is included such as
Lower step：
(1) the pure FeC of appropriate chemistry is taken2O4・2H2O、Li2CO3、NH4H2PO4, metal Mn powder and metal Pr powder as raw material,
According to Li1-xPr xFe1-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 more than 5 hours；
(4) continue said mixture raising temperature to 600 DEG C, then constant temperature more than 10 hours；
(5) furnace cooling after the completion of reacting, collect powder and produce product.
Preferentially, step (1) in, according to Li0.97Pr0.03Fe0.85Mn0.15PO4Atomic ratio dispensing.
Preferentially, step (2) in, protected in mechanical milling process with argon gas.
Preferentially, step (2) in, ball milling speed set 300-400 revs/min, Ball-milling Time is 8-12 hours.
Preferentially, step (3) in, the control of 300 DEG C of constant temperature times is in 6-8 hours.
Preferentially, 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；
(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 Pr powder as raw material, according to
Li0.97Pr0.03Fe0.85Mn0.15PO4Atom 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 300 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 、Li2CO3、NH4H2PO4, metal Mn powder and metal Pr powder as raw material, according to
Li0.99Pr0.01Fe0.9Mn0.1PO4Atom 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 350 revs/min, after ball milling 11h, 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 、Li2CO3、NH4H2PO4, metal Mn powder and metal Pr powder as raw material, according to
Li0.9Pr0.1Fe0.8Mn0.2PO4Atom 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 12h, 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 preparation technology of electrode material, it is characterised in that the preparation technology is carried out as follows：
(1) the pure FeC of appropriate chemistry is taken2O4・2H2O、Li2CO3、NH4H2PO4, metal Mn powder and metal Pr powder as raw material,
According to Li1-xPr xFe1-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 more than 5 hours；
(4) continue said mixture raising temperature to 600 DEG C, then constant temperature more than 10 hours；
(5) furnace cooling after the completion of reacting, collect powder and produce product.
A kind of 2. preparation technology of electrode material as claimed in claim 1, it is characterised in that step (1) in, atom ratio is pressed
According to Li0.97La0.03Fe0.85Mn0.15PO4Atomic ratio dispensing.
A kind of 3. preparation technology of electrode material as described in claim 1 or 2, it is characterised in that step (2) in, ball milling mistake
Protected in journey with argon gas.
A kind of 4. preparation technology of electrode material as described in claim 1 or 2, it is characterised in that step (2) in, ball milling speed
Degree sets 300-400 revs/min, and Ball-milling Time is 8-12 hours.
A kind of 5. preparation technology of electrode material as described in claim 1 or 2, it is characterised in that step (3) in, 300 DEG C
Constant temperature time was controlled in 6-8 hours.
A kind of 6. preparation technology of electrode material as described in claim 1 or 2, it is characterised in that step (4) in, 600 DEG C
Constant temperature time was controlled in 15-20 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710553784.4A CN107834059A (en) | 2017-07-08 | 2017-07-08 | A kind of preparation technology of novel composite electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710553784.4A CN107834059A (en) | 2017-07-08 | 2017-07-08 | A kind of preparation technology of novel composite electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107834059A true CN107834059A (en) | 2018-03-23 |
Family
ID=61642998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710553784.4A Withdrawn CN107834059A (en) | 2017-07-08 | 2017-07-08 | A kind of preparation technology of novel composite electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107834059A (en) |
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 |
| US20100171071A1 (en) * | 2009-01-08 | 2010-07-08 | Hengdian Group Dmegc Magnetic Limited Company | Lithium iron phosphate having oxygen vacancy and doped in the position of fe and method of quick solid phase sintering for the same |
| 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 |
| 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 CN201710553784.4A patent/CN107834059A/en not_active Withdrawn
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 |
| US20100171071A1 (en) * | 2009-01-08 | 2010-07-08 | Hengdian Group Dmegc Magnetic Limited Company | Lithium iron phosphate having oxygen vacancy and doped in the position of fe and method of quick solid phase sintering for the same |
| 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 |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108987697B (en) | Preparation method of olivine type manganese phosphate lithium ion battery positive electrode material with high specific energy | |
| CN105609763A (en) | Rare earth Y doped lithium iron phosphate electrode material and preparation method thereof | |
| CN105428652A (en) | Novel rare-earth-lithium iron phosphate composite electrode material and preparation method thereof | |
| CN105514428A (en) | Composite electrode material and preparation technology thereof | |
| CN105576237A (en) | Zn-added lithium ion battery cathode material and preparation method thereof | |
| CN105591103A (en) | Modification process of lithium ion battery cathode material | |
| CN107834059A (en) | A kind of preparation technology of novel composite electrode material | |
| CN107834025A (en) | A kind of compound lithium ion electrode material | |
| CN107827092A (en) | A kind of electrode material | |
| CN107834026A (en) | The combination electrode material and its preparation technology of a kind of high conductivity | |
| CN107834067A (en) | A kind of Cu, Er codope combination electrode material and preparation method thereof | |
| CN108232190A (en) | A kind of doped lanthanum, the lithium iron phosphate electrode material of terbium | |
| CN105609714A (en) | Positive electrode material added with Cr element of lithium ion battery and preparation method | |
| CN107834029A (en) | A kind of doping Cr combination electrode material and its preparation technology | |
| CN105514427A (en) | Ti doped LiFe(1-x)TixPO4 electrode material | |
| CN105609764A (en) | High-stability rare earth-lithium iron phosphate composite electrode material | |
| CN108206272A (en) | A kind of LiMn for adulterating Gd2O4Electrode material and preparation method thereof | |
| CN107834066A (en) | A kind of high conductivity combination electrode material and technique for adulterating manganese | |
| CN105428651A (en) | Rare-earth cerium-doped lithium iron phosphate composite electrode material | |
| CN108206273A (en) | A kind of LiMn for adulterating Tb2O4Electrode material | |
| CN108203118A (en) | A kind of novel LiMn2O4Electrode material and its preparation process | |
| CN107834028A (en) | A kind of combination electrode material for adulterating vanadium | |
| CN108615883A (en) | A kind of Li of doping Yb, Gd1-（x+y）FeYbxGdyPO4Combination electrode material | |
| CN108258202A (en) | A kind of manganic acid lithium electrode material and its preparation process for adulterating terbium and dysprosium | |
| CN108615876A (en) | A kind of li-ion electrode materials of addition La elements |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180323 |
|
| WW01 | Invention patent application withdrawn after publication |