CN110104625A - A kind of preparation method of additive Mn copper phosphate plus plate material - Google Patents
A kind of preparation method of additive Mn copper phosphate plus plate material Download PDFInfo
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- CN110104625A CN110104625A CN201910439703.7A CN201910439703A CN110104625A CN 110104625 A CN110104625 A CN 110104625A CN 201910439703 A CN201910439703 A CN 201910439703A CN 110104625 A CN110104625 A CN 110104625A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
A kind of preparation method of additive Mn copper phosphate plus plate material.Copper oxide is added in deionized water and obtains suspending liquid A；Soluble phosphate is dissolved in solution A and freezes to obtain solid B；Solid B is freeze-dried, phosphate is recrystallized in CuO surface, obtains mixture C；Mixture C, which is put into agate mortar grinding, makes it uniformly be mixed to get sample D；Four water manganese acetates and tetrahydrate manganese chloride are dissolved in the water, and are added dropwise in sample D, ball milling after drying obtains presoma E；Presoma E is placed in magnetic boat and is heat-treated to obtain Mn doping phosphoric acid copper Cu3(PO4)2Positive electrode.The present invention makes cupric phosphate be wrapped in CuO surface with the method for dissolving again crystallization, obtains the high predecessor of degree of purity.The present invention is not needing under conditions of having protective atmosphere (including vacuum environment) simultaneously, and after manganese source liquid phase doping, ball milling obtains product, is heat-treated by way of directly heating up, and soaking time is short, so that it may obtain the material of expected pattern.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of preparation method of additive Mn copper phosphate plus plate material.
Background technique
Concern with various countries to fossil energy crisis and problem of environmental pollution is researched and developed, using High-performance green lithium ion
Battery, it has also become one of hot spot of scientists from all over the world's research [tetra- major class anode material for lithium-ion batteries of Qu Bo, Zhang Bing, Zheng Shengnan
Be in progress [J] power technology, 2016,40 (7): 1515-1518.].The chemical property of lithium ion battery and used electrode
Material has very big relationship, and for cathode, positive electrode develops more slow.Current research work is mainly concentrated
In layered oxide, spinel structure compound, polyanionic compound and other positive electrodes etc. [Wan Yang, Zheng's buckwheat is robust and sturdy,
It rents honest quick lithium ion battery anode material manganese lithium phosphate progress [J] chemistry journal, 2014,72 (5): 537-551.].Section
Grinding worker mainly utilizes the methods of surface cladding, doping and component design to have nothing to existing material modification and positive research and development
[synthesis of Wan Yi, Guo Xiuping, Wang Min additive Mn LiFePO4 and chemical property are ground the composite material of setting or porous structure
Study carefully [J] Xuzhou Engineering Institute journal (natural science edition), 2017 (3)].
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of additive Mn copper phosphate plus plate material, i.e., draw in cupric phosphate
Enter micro manganese ion, interstitial void space and internal transmission characteristic can be adjusted by the method for doping vario-property, reduces ion and move
Resistance is moved, the ionic conductivity and electron conduction of phosphate material are improved, so as to improve the chemical property of material.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
1) 1g copper oxide is added to ultrasonic disperse in 10~30ml deionized water makes copper oxide be uniformly dispersed in water, obtains
To suspending liquid A；
It 2) is that 1:0.6~2 take soluble phosphate molten in magnetic agitation by the mass ratio of soluble phosphate and copper oxide
In solution A, then be added dropwise phosphoric acid adjust its pH value be 4~6 after, be put into refrigerator and freeze to obtain solid B；
3) solid B is freeze-dried, recrystallizes phosphate in CuO surface, obtains mixture C；
4) mixture C is put into agate mortar grinding makes it uniformly be mixed to get sample D；
It 5) is that 10~20:1 takes four water manganese acetates and four by the molar ratio of copper oxide and four water manganese acetates and tetrahydrate manganese chloride
Water manganese chloride is dissolved in 5~20mL water, and is added dropwise in sample D, obtains phosphate, copper oxide, manganese acetate after dry
Mixture, by mixture with 300~600r min-1Revolving speed ball milling, mix them thoroughly, obtain presoma E；
6) sample E is placed in magnetic boat, covers lid, with 5~10 DEG C of min in box high temperature sintering furnace-1Heating speed
Rate is heat-treated to obtain Mn doping phosphoric acid copper Cu from room temperature to 600~800 DEG C3(PO4)2Positive electrode.
10~30min of the step 1) ultrasonic disperse.
Step 2) the soluble phosphate is sodium phosphate or ammonium hydrogen phosphate.
1~3h of the step 2) magnetic agitation.
The step 2) freezing 12~for 24 hours.
The step 3) freeze-drying 12~for 24 hours.
Step 5) the ball milling uses planetary ball mill.
The step 6) is heat-treated 10~30min.
Advantages of nontoxic raw materials of the present invention is pollution-free, and experimental program is simple to operation.With the method for dissolving again crystallization
So that cupric phosphate is wrapped in CuO surface, the high predecessor of degree of purity is obtained.The present invention is not needing having protection gas simultaneously
Under conditions of atmosphere (including vacuum environment), after manganese source liquid phase doping, ball milling obtains product, hot by way of directly heating up
Processing, soaking time are short, so that it may obtain the material of expected pattern.
Beneficial effect:
1) present invention is obtaining the rodlike and spherical cupric phosphate to interconnect of morphology controllable just by the incorporation of control manganese
Pole material；
2) present invention by liquid phase method prepares predecessor, can two-phase uniformly be mixed, experimental implementation it is simple and easy and
It is raw materials used environmental-friendly, it is pollution-free.
Detailed description of the invention
Fig. 1 is the SEM figure of additive Mn copper phosphate plus plate material prepared by the embodiment of the present invention 1.
Fig. 2 is the XRD diagram of additive Mn copper phosphate plus plate material prepared by the embodiment of the present invention 1.
Fig. 3 is the performance map of additive Mn copper phosphate plus plate material prepared by the embodiment of the present invention 1.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and embodiments.
Embodiment 1:
1) 1g copper oxide is added to ultrasonic disperse 10min in 10ml deionized water and obtains suspending liquid A；
2) it is that 1:0.6 takes sodium phosphate magnetic agitation 1h to be dissolved in solution A by the mass ratio of sodium phosphate and copper oxide, then drips
Add phosphoric acid adjust its pH value be 4 after, be put into refrigerator freeze 12h obtain solid B；
3) solid B is freeze-dried 12h, recrystallizes phosphate in CuO surface, obtains mixture C；
4) mixture C is put into agate mortar grinding makes it uniformly be mixed to get sample D；
It 5) is that 10:1 takes four water manganese acetates and four water chlorine by the molar ratio of copper oxide and four water manganese acetates and tetrahydrate manganese chloride
Change manganese to be dissolved in 5mL water, and be added dropwise in sample D, obtains the mixture of phosphate, copper oxide, manganese acetate after dry,
By mixture with 300r min-1Revolving speed ball milling, mix them thoroughly, obtain presoma E；
6) sample E is placed in magnetic boat, covers lid, with 5 DEG C of min in box high temperature sintering furnace-1Heating rate from
Room temperature obtains Mn doping phosphoric acid copper Cu to 600 DEG C of heat treatment 10min3(PO4)2Positive electrode.
Referring to Fig. 1, the JSM-6700F type scanning electron microscope that product manufactured in the present embodiment Japanese firm is produced
It is observed, as can be seen that cupric phosphate is with rodlike and spherical topographic profile from SEM figure, the connected composition of intersection between them
Conductive network framework
Referring to fig. 2, product manufactured in the present embodiment Rigaku D/max2000PCX- x ray diffractometer x is analyzed, hair
Existing sample is Mn doping phosphoric acid copper Cu3(PO4)2。
Referring to Fig. 3, in 50mAg-1Current density under, first circle discharge capacity be 306mAhg-1, after circulation 30 is enclosed,
Its reversible capacity is 154mAhg-1。
Embodiment 2:
1) 1g copper oxide is added to ultrasonic disperse 20min in 20ml deionized water and obtains suspending liquid A；
It 2) is that 1:1.2 takes ammonium hydrogen phosphate magnetic agitation 2h to be dissolved in solution A by the mass ratio of ammonium hydrogen phosphate and copper oxide, so
Afterwards be added dropwise phosphoric acid adjust its pH value be 5 after, be put into refrigerator freeze 18h obtain solid B；
3) solid B is freeze-dried 18h, recrystallizes phosphate in CuO surface, obtains mixture C；
4) mixture C is put into agate mortar grinding makes it uniformly be mixed to get sample D；
It 5) is that 15:1 takes four water manganese acetates and four water chlorine by the molar ratio of copper oxide and four water manganese acetates and tetrahydrate manganese chloride
Change manganese to be dissolved in 12mL water, and be added dropwise in sample D, obtains the mixing of phosphate, copper oxide, manganese acetate after dry
Object, by mixture with 450r min-1Revolving speed ball milling, mix them thoroughly, obtain presoma E；
6) sample E is placed in magnetic boat, covers lid, with 8 DEG C of min in box high temperature sintering furnace-1Heating rate from
Room temperature obtains Mn doping phosphoric acid copper Cu to 700 DEG C of heat treatment 20min3(PO4)2Positive electrode.
Embodiment 3:
1) 1g copper oxide is added to ultrasonic disperse 25min in 30ml deionized water and obtains suspending liquid A；
2) it is that 1:2 takes sodium phosphate magnetic agitation 3h to be dissolved in solution A by the mass ratio of sodium phosphate and copper oxide, is then added dropwise
Phosphoric acid adjust its pH value be 6 after, be put into refrigerator freeze for 24 hours solid B；
3) it for 24 hours by solid B freeze-drying, recrystallizes phosphate in CuO surface, obtains mixture C；
4) mixture C is put into agate mortar grinding makes it uniformly be mixed to get sample D；
It 5) is that 20:1 takes four water manganese acetates and four water chlorine by the molar ratio of copper oxide and four water manganese acetates and tetrahydrate manganese chloride
Change manganese to be dissolved in 20mL water, and be added dropwise in sample D, obtains the mixing of phosphate, copper oxide, manganese acetate after dry
Object, by mixture with 600r min-1Revolving speed ball milling, mix them thoroughly, obtain presoma E；
6) sample E is placed in magnetic boat, covers lid, with 10 DEG C of min in box high temperature sintering furnace-1Heating rate from
Room temperature obtains Mn doping phosphoric acid copper Cu to 800 DEG C of heat treatment 30min3(PO4)2Positive electrode.
Embodiment 4:
1) 1g copper oxide is added to ultrasonic disperse 15min in 15ml deionized water and obtains suspending liquid A；
It 2) is that 1:1 takes ammonium hydrogen phosphate magnetic agitation 3h to be dissolved in solution A by the mass ratio of ammonium hydrogen phosphate and copper oxide, then
Be added dropwise phosphoric acid adjust its pH value be 6 after, be put into refrigerator freeze 20h obtain solid B；
3) solid B is freeze-dried 15h, recrystallizes phosphate in CuO surface, obtains mixture C；
4) mixture C is put into agate mortar grinding makes it uniformly be mixed to get sample D；
It 5) is that 13:1 takes four water manganese acetates and four water chlorine by the molar ratio of copper oxide and four water manganese acetates and tetrahydrate manganese chloride
Change manganese to be dissolved in 13mL water, and be added dropwise in sample D, obtains the mixing of phosphate, copper oxide, manganese acetate after dry
Object, by mixture with 500r min-1Revolving speed ball milling, mix them thoroughly, obtain presoma E；
6) sample E is placed in magnetic boat, covers lid, with 6 DEG C of min in box high temperature sintering furnace-1Heating rate from
Room temperature obtains Mn doping phosphoric acid copper Cu to 750 DEG C of heat treatment 15min3(PO4)2Positive electrode.
Embodiment 5:
1) 1g copper oxide is added to ultrasonic disperse 30min in 25ml deionized water and obtains suspending liquid A；
2) it is that 1:1.8 takes sodium phosphate magnetic agitation 2h to be dissolved in solution A by the mass ratio of sodium phosphate and copper oxide, then drips
Add phosphoric acid adjust its pH value be 5 after, be put into refrigerator freeze 15h obtain solid B；
3) solid B is freeze-dried 20h, recrystallizes phosphate in CuO surface, obtains mixture C；
4) mixture C is put into agate mortar grinding makes it uniformly be mixed to get sample D；
It 5) is that 18:1 takes four water manganese acetates and four water chlorine by the molar ratio of copper oxide and four water manganese acetates and tetrahydrate manganese chloride
Change manganese to be dissolved in 18mL water, and be added dropwise in sample D, obtains the mixing of phosphate, copper oxide, manganese acetate after dry
Object, by mixture with 400r min-1Revolving speed ball milling, mix them thoroughly, obtain presoma E；
6) sample E is placed in magnetic boat, covers lid, with 9 DEG C of min in box high temperature sintering furnace-1Heating rate from
Room temperature obtains Mn doping phosphoric acid copper Cu to 650 DEG C of heat treatment 25min3(PO4)2Positive electrode.
Claims (8)
1. a kind of preparation method of additive Mn copper phosphate plus plate material, it is characterised in that the following steps are included:
1) 1g copper oxide is added to ultrasonic disperse in 10~30ml deionized water makes copper oxide be uniformly dispersed in water, is hanged
Supernatant liquid A；
2) to be that 1:0.6~2 take soluble phosphate to be dissolved in magnetic agitation by the mass ratio of soluble phosphate and copper oxide molten
In liquid A, then be added dropwise phosphoric acid adjust its pH value be 4~6 after, be put into refrigerator and freeze to obtain solid B；
3) solid B is freeze-dried, recrystallizes phosphate in CuO surface, obtains mixture C；
4) mixture C is put into agate mortar grinding makes it uniformly be mixed to get sample D；
It 5) is that 10~20:1 takes four water manganese acetates and four water chlorine by the molar ratio of copper oxide and four water manganese acetates and tetrahydrate manganese chloride
Change manganese to be dissolved in 5~20mL water, and be added dropwise in sample D, obtained after dry phosphate, copper oxide, manganese acetate it is mixed
Object is closed, by mixture with 300~600r min-1Revolving speed ball milling, mix them thoroughly, obtain presoma E；
6) sample E is placed in magnetic boat, covers lid, with 5~10 DEG C of min in box high temperature sintering furnace-1Heating rate from
Room temperature is heat-treated to obtain Mn doping phosphoric acid copper Cu to 600~800 DEG C3(PO4)2Positive electrode.
2. the preparation method of additive Mn copper phosphate plus plate material according to claim 1, it is characterised in that: the step 1)
10~30min of ultrasonic disperse.
3. the preparation method of additive Mn copper phosphate plus plate material according to claim 1, it is characterised in that: the step 2)
Soluble phosphate is sodium phosphate or ammonium hydrogen phosphate.
4. the preparation method of additive Mn copper phosphate plus plate material according to claim 1, it is characterised in that: the step 2)
1~3h of magnetic agitation.
5. the preparation method of additive Mn copper phosphate plus plate material according to claim 1, it is characterised in that: the step 2)
Freezing 12~for 24 hours.
6. the preparation method of additive Mn copper phosphate plus plate material according to claim 1, it is characterised in that: the step 3)
Freeze-drying 12~for 24 hours.
7. phosphoric acid oxygen copper according to claim 1/copper oxide/manganese phosphate three-phase composite material preparation method, feature
Be: the step 5) ball milling uses planetary ball mill.
8. the preparation method of additive Mn copper phosphate plus plate material according to claim 1, it is characterised in that: the step 6)
It is heat-treated 10~30min.
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| CN201910439703.7A CN110104625B (en) | 2019-05-24 | 2019-05-24 | Preparation method of manganese-doped copper phosphate positive electrode material |
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| CN201910439703.7A CN110104625B (en) | 2019-05-24 | 2019-05-24 | Preparation method of manganese-doped copper phosphate positive electrode material |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891177A (en) * | 2010-07-05 | 2010-11-24 | 华中农业大学 | Method for preparing manganese phosphate material |
| CN105793196A (en) * | 2013-11-11 | 2016-07-20 | 化学制造布敦海姆两合公司 | Doped copper (ii) hydroxide phosphate, method for producing same, and use thereof |
| CN107611418A (en) * | 2017-09-29 | 2018-01-19 | 陕西科技大学 | A kind of particles self assemble cubic Cu3(PO4)2/Cu2P2O7The preparation method of combination electrode material |
-
2019
- 2019-05-24 CN CN201910439703.7A patent/CN110104625B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891177A (en) * | 2010-07-05 | 2010-11-24 | 华中农业大学 | Method for preparing manganese phosphate material |
| CN105793196A (en) * | 2013-11-11 | 2016-07-20 | 化学制造布敦海姆两合公司 | Doped copper (ii) hydroxide phosphate, method for producing same, and use thereof |
| CN107611418A (en) * | 2017-09-29 | 2018-01-19 | 陕西科技大学 | A kind of particles self assemble cubic Cu3(PO4)2/Cu2P2O7The preparation method of combination electrode material |
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