CN107834066A - A kind of high conductivity combination electrode material and technique for adulterating manganese - Google Patents
A kind of high conductivity combination electrode material and technique for adulterating manganese Download PDFInfo
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- CN107834066A CN107834066A CN201710553882.8A CN201710553882A CN107834066A CN 107834066 A CN107834066 A CN 107834066A CN 201710553882 A CN201710553882 A CN 201710553882A CN 107834066 A CN107834066 A CN 107834066A
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- electrode material
- high conductivity
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- powder
- 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
- H01M4/58—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
- 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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- 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 high conductivity combination electrode material and technique for adulterating manganese.The electrode material is with FeC2O4・2H2O、LiOH、NH4H2PO4, Tb powder and Mn powder as raw material, it is first pressed into Li1‑xTb xFe1‑yMnyPO4Ratio dispensing; the raw mixture prepared is poured into ball grinder again; mechanical ball mill is carried out under conditions of protective gas; ball milling takes out ball milling micro mist after terminating; in the environment of protective gas nitrogen; micro mist is placed in high temperature sintering for a period of time, cooled down after the completion of reaction, takes out and collects made micro mist.This process regulation is simple, and the conductive forthright improvement of doping manganese pair is obvious, has preferable application prospect.
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
LiFePO4Belong to newer positive electrode, its is safe, cost is relatively low, it is believed that be to prepare long-life, Gao Gong
Rate, high security, one of the optimal positive electrode of lithium-ion-power cell of low cost.LiFePO4With six somewhat distorted
Square close packed array structure, belong to rhombic system, space group Pnma.In the a-c planes where lithium atom, include
PO4Tetrahedron, which limits the mobile space of lithium ion, causes lithium ion mobility speed and electronic conductivity relatively low, this
It is LiFePO4The inherent defect of material.
In order to improve LiFePO4Performance, often add rare earth element, rare earth element is metal material " vitamin ",
There play the role of to the performance for improving metal material to be special.Rare earth element can instead of Li position, be dissolved into olive well
In stone structure.But rare earth element is only added, to LiFePO4Conductance performance improvement unobvious, which has limited LiFePO4
Electrode material is further applied.
The content of the invention
The present invention prepares a kind of addition rare earth Tb elements and Mn elements by ball-milling technology and high temperature solid-state method reaction
LiFePO4Combination electrode material, make up LiFePO4Deficiency, improve LiFePO4Conduction and charge-discharge performance.The preparation technology
Comprise the following steps：
(1) appropriate chemical pure FeC is taken2O4・2H2O、LiOH、NH4H2PO4, Tb powder and Mn powder as raw material, according to Li1-xTb x
Fe1-y MnyPO4（0.01≤x≤0.1, 0. 1≤y≤0.3）Atom ratio prepare raw material；
(2) the raw mixture prepared is poured into ball grinder, mechanical ball mill is carried out under conditions of protective gas；
(3) ball milling micro mist is taken out after ball milling terminates, in the environment of protective gas nitrogen, micro mist is placed in 300 DEG C of conditions of temperature and entered
Row Isothermal sinter is for a period of time；
(4) temperature is increased to 700 DEG C again, Isothermal sinter is for a period of time；
(5) furnace cooling after the completion of reacting, collect powder and produce electrode material micro mist.
Preferentially, step (1) in, according to Li0.97Tb0.03Fe0.85Mn0.15PO4Atomic ratio dispensing.
Preferentially, step (2) in, protected in mechanical milling process with argon gas, ball milling speed set 200-300 revs/min
Clock, Ball-milling Time are 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 700 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；
(2) condition control is simple, it is easy to accomplish industrialization.
Embodiment one：
With the pure FeC of chemistry2O4・2H2O、LiOH、NH4H2PO4, Tb powder and Mn 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 700 DEG C, constant temperature 15 hours, last furnace cooling, powder is collected and produces product.
Embodiment two：
With the pure FeC of chemistry2O4・2H2O、LiOH、NH4H2PO4, Tb powder and Mn 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 700 DEG C, constant temperature 18 hours, last furnace cooling, powder is collected and produces product.
Embodiment three：
With the pure FeC of chemistry2O4・2H2O、LiOH、NH4H2PO4, Tb powder and Mn 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 700 DEG C, constant temperature 20 hours, last furnace cooling, powder is collected and produces product.
Claims (5)
1. a kind of high conductivity combination electrode material for adulterating manganese, it is characterised in that the preparation method of the electrode material is by following step
It is rapid to carry out：
(1) appropriate chemical pure FeC is taken2O4・2H2O、LiOH、NH4H2PO4, Tb powder and Mn powder as raw material, according to Li1-xTb x
Fe1-y MnyPO4（0.01≤x≤0.1, 0. 1≤y≤0.3）Atom ratio prepare raw material；
(2) the raw mixture prepared is poured into ball grinder, mechanical ball mill is carried out under conditions of protective gas；
(3) ball milling micro mist is taken out after ball milling terminates, in the environment of protective gas nitrogen, micro mist is placed in 300 DEG C of conditions of temperature and entered
Row Isothermal sinter is for a period of time；
(4) temperature is increased to 700 DEG C again, Isothermal sinter is for a period of time；
(5) furnace cooling after the completion of reacting, collect powder and produce electrode material micro mist.
2. a kind of high conductivity combination electrode material for adulterating manganese as claimed in claim 1, it is characterised in that prepared in material
The step of (1) in, according to Li0.97Tb0.03Fe0.85Mn0.15PO4Atomic ratio dispensing.
3. a kind of high conductivity combination electrode material for adulterating manganese as described in claim 1 or 2, it is characterised in that in material
The step of prepared by material (2) in, protected in mechanical milling process with argon gas, ball milling speed sets 200-300 revs/min, during ball milling
Between be 10-12 hours.
4. a kind of high conductivity combination electrode material for adulterating manganese as described in claim 1 or 2, it is characterised in that in material
Material prepare the step of (3) in, step (3) in, 300 DEG C of Isothermal sinter time controls are in 6-7 hours.
5. a kind of high conductivity combination electrode material for adulterating manganese as described in claim 1 or 2, it is characterised in that in material
The step of prepared by material (4) in, the control of 700 DEG C of constant temperature times is in 15-20 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710553882.8A CN107834066A (en) | 2017-07-09 | 2017-07-09 | A kind of high conductivity combination electrode material and technique for adulterating manganese |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710553882.8A CN107834066A (en) | 2017-07-09 | 2017-07-09 | A kind of high conductivity combination electrode material and technique for adulterating manganese |
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| Publication Number | Publication Date |
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| CN107834066A true CN107834066A (en) | 2018-03-23 |
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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 |
| 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
- 2017-07-09 CN CN201710553882.8A patent/CN107834066A/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 |
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Application publication date: 20180323 |