CN106784726A - Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof - Google Patents
Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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
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Abstract
It is modified lithium-rich manganese-based layered lithium ion battery positive electrode the invention discloses a kind of vanadyl phosphate lithium, its chemical general formula is xLi2MnO3·(1‑x)LiMO2·yLiVOPO4, wherein, 0.1≤x≤0.9, M is Mn, Co and Ni, and the percentage that y accounts for x is 0.1~99%；Including manganese raw material, nickel raw material, cobalt raw material, lithium salts, phosphorus source, vanadium source, complexing agent and reducing agent.Its preparation method is：Lithium-rich manganese-based layered lithium ion battery positive electrode and vanadyl phosphate lithium presoma are prepared using sol-gal process, then vanadyl phosphate lithium is prepared using collosol and gel liquid phase cladding process or grinding solid phase cladding process and be modified lithium-rich manganese-based layered lithium ion battery positive electrode.The characteristic such as the present invention is using vanadyl phosphate lithium energy density is high, platform stable, decay are slow improves the electrochemical stability and cyclical stability of anode material for lithium-ion batteries, significantly improves high rate performance, improves the problem of platform decay.
Description
Technical field
The present invention relates to lithium ion battery preparation field, and in particular to vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion
Cell positive material and preparation method thereof.
Background technology
Energy crisis and environmental pollution have become the serious threat of human kind sustainable development, and Renewable Energy Development gesture exists
Must go.Fully the clean energy resource such as exploitation solar energy, wind energy, Hydrogen Energy, tide energy has for the sustainable development in the whole world and weighs very much
The meaning wanted.But these energy are discontinuous, so electrochmical power source shows the device that energy is changed and stored as a kind of
Obtain extremely important.
In portable, large-scale application high-energy-density, the reliable lithium ion of lightweight and security
Battery.For lithium ion battery, positive electrode is always its core.Up to the present, LiCoO2Extensively should
For the positive electrode of commercial li-ion battery, it is easily prepared, and with good chemical property, but it is but only showed
Go out theoretical capacity half (140mAhg-1) reversible capacity, and Co is a kind of poisonous and costly element, therefore its cost
These problems high and toxic are all limitation LiCoO2Factor as preferable positive electrode.LiMn2O4It is typical spinel structure
Positive electrode, spinelle LiMn2O4With than LiCoO2Low cost, hypotoxicity and high rate capability and widely ground by everybody
Study carefully；However, spinelle LiMn2O4Capacity attenuation than more serious, especially at high temperature, there is provided capacity also can be more lower slightly,
Only 120mAhg-1Left and right.LiFePO4Main way is electrokinetic cell, Fe in nature rich reserves, toxicity also than Co,
Ni, Mn are low, and the good characteristic such as its long-life, security and high temperature resistant causes that it attracts attention.But, LiFePO4Material
Electronic conductivity is low by (10 at room temperature for material-9S/cm), poorly conductive, tap density is low, poor performance at low temperatures, etc. capacity ferric phosphate
The volume of lithium battery is greater than the lithium ion batteries such as cobalt acid lithium, therefore does not have advantage in terms of minicell, disadvantage mentioned above limit
Its extensive use is made.
So how reduces cost, improve security, improve capacity into research work subject matter.By substantial amounts of
Research, researcher substitutes Co with Ni, Mn, prepares a kind of layered cathode material Li [Li0.2Mn0.54Ni0.13Co0.13]O2, by
Larger content, referred to as lithium-rich manganese-based anode material are occupied in Mn elements.In the positive electrode studied, lithium-rich anode
Material xLi2MnO3·(1-x)LiMO2230mAhg can be provided when more than 2.5V operating voltages-1High power capacity above, turns into
Most promising positive electrode of new generation.The wherein effect of Co can reduce cation mixing occupy-place, the layer of effective stabilizing material
Shape structure, reduces impedance value, improves electrical conductivity.Mn is introduced, material cost can be not only reduced, but also material can be improved
Safety and stability；Introducing Ni can improve the capacity of material.
In existing lithium-rich manganese-based layered cathode material, Li+Ionic diffusion coefficient is very low, and only 10-14cm2s-1Left and right, makes
The electronic conductivity for obtaining material is very low.Therefore this material still has many problem demanding prompt solutions：Less efficient first,
High rate capability that low electronic conductance is caused is poor, long circulating stability is poor, platform decay etc..
The content of the invention
For problems of the prior art, lithium-rich manganese-based stratiform is being modified just it is an object of the invention to vanadyl phosphate lithium
Pole material, its discharge platform decay is slow, good rate capability.
It is modified lithium-rich manganese-based layered cathode material and its system it is a further object to provide a kind of vanadyl phosphate lithium
Preparation Method, the vanadyl phosphate lithium is modified lithium-rich manganese-based layered cathode material discharge platform decay slowly, good rate capability.
In order to achieve the above object, the present invention is achieved using following technical scheme.
(1) vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that its chemistry is logical
Formula xLi2MnO3·(1-x)LiMO2·yLiVOPO4, wherein, 0.1≤x≤0.9, M is Mn, Co and Ni, and the percentage that y accounts for x is
0.1-99%.
(2) vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that including following
Raw material components：Manganese raw material, nickel raw material, cobalt raw material, lithium salts, phosphorus source, vanadium source, complexing agent and reducing agent.
Preferably, the manganese raw material is manganese metal, Mn oxide, inorganic salts containing manganese, organic salt containing manganese or alcohol containing manganese
Salt.
It is further preferred that the manganese raw material is manganese acetate, manganese nitrate, manganese sulfate, formic acid manganese or manganese acetate.
Preferably, the nickel raw material is metallic nickel, nickel oxide, nickeliferous inorganic salts, nickeliferous organic salt or nickeliferous alcohol
Salt.
It is further preferred that the nickel raw material is nickel acetate, nickel nitrate, nickel sulfate, nickel formate or nickel acetate.
Preferably, the cobalt raw material is metallic cobalt, cobalt/cobalt oxide, inorganic salts containing cobalt, organic salt containing cobalt or alcohol containing cobalt
Salt.
It is further preferred that the cobalt raw material is cobalt acetate, cobalt nitrate, cobaltous sulfate, cobaltous formate or cobalt acetate.
Preferably, the lithium salts is oxidate for lithium, inorganic salts containing lithium, organic salt containing lithium or containing lithium alkoxide.
It is further preferred that the lithium salts is lithium nitrate, lithium acetate, lithium formate, lithium hydroxide or lithium carbonate.
Preferably, phosphorus source is phosphorous organic phosphate or phosphorous organophosphorus ester.
It is further preferred that phosphorus source is ammonium dihydrogen phosphate, ammonium metaphosphate, phosphoric acid or triethyl phosphate.
Preferably, the vanadium source is barium oxide, organic vanadate, organic vanadium acid esters.
It is further preferred that the vanadium source is vanadic anhydride, ammonium vanadate.
Preferably, the complexing agent is alcamines complexing agent, hydroxycarboxylic acid complexing agent, organic phosphate complexing
Agent or polyacrylic complexing agent.
It is further preferred that the complexing agent is citric acid, acetylacetone,2,4-pentanedione, ethylenediamine tetra-acetic acid, sucrose or glucose.
Preferably, the reducing agent is organic acid reducing agent, inorganic acids reducing agent or alcohols reducing agent.
It is further preferred that the reducing agent is oxalic acid, citric acid, nitric acid.
Preferably, in the lithium salts, manganese raw material, nickel raw material and cobalt raw material, Li+、Mn2+、Ni2+With Co2+Mol ratio
It is (1.1~1.9)：(0.3997~0.9333)：(0.2997~0.0333)：(0.2997~0.0333).
Preferably, the M and the mol ratio of complexing agent are 1:1~1:2.
(3) a kind of vanadyl phosphate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, its feature
It is to comprise the following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared using sol-gal process：Manganese raw material, nickel is former
Material, cobalt raw material are dissolved in liquid flux successively, add complexing agent, lithium salts, and heating water bath, stirring reaction obtain presoma molten
Glue, 100 DEG C are incubated 24-36h, finally thermally treated to obtain lithium-rich manganese-based layered lithium ion battery positive electrode；
Step 2, vanadyl phosphate lithium solution is prepared using sol-gal process：Vanadium source and reducing agent are dissolved in liquid flux,
Lithium salts, phosphorus source are added, heating water bath, stirring reaction form colloidal sol, obtain vanadyl phosphate lithium solution；
Step 3, prepares vanadyl phosphate lithium and is modified lithium-rich manganese-based layered lithium ion battery using collosol and gel liquid phase cladding process
Positive electrode：By in lithium-rich manganese-based layered cathode material addition vanadyl phosphate lithium solution, agitated, ultrasonic, negative pressure impregnation is obtained
Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor, finally by the modified richness of the vanadyl phosphate lithium
Li Meng basic units shape precursor of lithium ionic cell positive material dries 12-24h for 70 DEG C in atmosphere, then is heat-treated, and obtains final product.
Preferably, in step 1, the temperature of the heating water bath is 50-90 DEG C, and the time of the stirring reaction is 3-
5h。
Preferably, in step 1, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere,
5h is calcined under the conditions of 450 DEG C successively, 12h is calcined under the conditions of 900 DEG C.
Preferably, in step 1 and step 2, the liquid flux is deionized water.
Preferably, in step 2, the temperature of the heating water bath is 70-80 DEG C, and the time of the stirring reaction is
0.5-2h。
Preferably, in step 3, the evacuated pressure of the negative pressure impregnation is 0.05-0.08MPa, and the time is 1-
12h。
Preferably, in step 3, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere,
4h is calcined under the conditions of 300 DEG C successively, 4h is calcined under the conditions of 500 DEG C.
(4) a kind of vanadyl phosphate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, its feature
It is to comprise the following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared using sol-gal process：Manganese raw material, nickel is former
Material, cobalt raw material are dissolved in liquid flux successively, add complexing agent, lithium salts, and heating water bath, stirring reaction obtain presoma molten
Glue, 100 DEG C are incubated 24-36h, finally thermally treated to obtain lithium-rich manganese-based layered lithium ion battery positive electrode；
Step 2, vanadyl phosphate lithium presoma is prepared using sol-gal process：Vanadium source and reducing agent are dissolved in liquid flux
In, lithium salts, phosphorus source are added, heating water bath, stirring reaction form colloidal sol, and drying obtains vanadyl phosphate lithium precursor powder.
Step 3, prepares vanadyl phosphate lithium and is modified lithium-rich manganese-based layered lithium ion battery positive pole using grinding solid phase cladding process
Material：The lithium-rich manganese-based layered lithium ion battery positive electrode is mixed with the vanadyl phosphate lithium precursor powder, and is ground
Mill is uniform, after heat treatment, obtains final product.
Preferably, in step 1, the temperature of the heating water bath is 50-90 DEG C, and the time of the stirring reaction is 3-
5h。
Preferably, in step 1 and step 2, the liquid flux is deionized water.
Preferably, in step 1, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere,
5h is calcined under the conditions of 450 DEG C successively, 12h is calcined under the conditions of 900 DEG C.
Preferably, in step 1, the temperature of the heating water bath is 70-80 DEG C, and the time of the stirring reaction is
0.5-2h。
Preferably, in step 2, the temperature of the drying is 50-100 DEG C.
Preferably, in step 3, the time of the grinding is 2-5h.
Preferably, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, successively 300
4h is calcined under the conditions of DEG C, 4h is calcined under the conditions of 500 DEG C.
Compared with prior art, beneficial effects of the present invention are：
Vanadyl phosphate lithium prepared by the present invention is modified lithium-rich manganese-based layered lithium ion battery positive electrode, using vanadyl phosphate
Lithium has energy density high, platform stable, decay the characteristic such as slow, improves the electrochemically stable of anode material for lithium-ion batteries
Property and cyclical stability, significantly improve the high rate performance of anode material for lithium-ion batteries, improve platform decay problem.
Brief description of the drawings
The present invention is described in further details with specific embodiment below in conjunction with the accompanying drawings.
Fig. 1 is modified the ESEM of lithium-rich manganese-based layered lithium ion battery positive electrode for the vanadyl phosphate lithium of embodiment 7
Figure；
Fig. 2 is modified lithium-rich manganese-based layered lithium ion battery positive electrode in 0.1C situations for the vanadyl phosphate lithium of embodiment 7
Preceding 9 charging and discharging curve figures down；In figure, abscissa is the specific capacity (sepecific capacity) of material, and unit is mAh/
G, ordinate is voltage (voltage), and unit is V；
Fig. 3 is modified the ESEM of lithium-rich manganese-based layered lithium ion battery positive electrode for the vanadyl phosphate lithium of embodiment 8
Figure；
Fig. 4 is modified lithium-rich manganese-based layered lithium ion battery positive electrode in 0.1C situations for the vanadyl phosphate lithium of embodiment 8
Preceding 9 charging and discharging curve figures down；In figure, abscissa is the specific capacity (sepecific capacity) of material, and unit is mAh/
G, ordinate is voltage (voltage), and unit is V.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
It will be appreciated that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the present invention.
Embodiment 1
A kind of vanadyl phosphate lithium of the invention is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, bag
Include following steps：
(1) manganese acetate 0.03997mol, cobalt acetate 0.02997mol, nickel acetate 0.02997mol are dissolved in 100mL successively
In deionized water, 0.09mol citric acids, 0.11mol lithium nitrates are added, it is 9 to adjust pH value with ammoniacal liquor afterwards, in 80 DEG C of water-baths
Under the conditions of, 3h is stirred, precursor sol is formed, 100 DEG C of insulation 24h in air, Muffle furnace calcining, Temperature Treatment is followed successively by 450
5h is calcined under the conditions of DEG C, 12h is calcined under the conditions of 900 DEG C；Lithium-rich manganese-based layered lithium ion battery positive electrode is obtained, it is powder
Shape.
(2) oxalic acid for weighing 0.000135mol is dissolved in 100mL deionized waters, by the vanadic anhydride of 0.000045mol
Add, under 70 DEG C of water bath conditions, stir 2h, 0.00009mol lithium nitrates finally add 0.00009mol ammonium dihydrogen phosphates
Enter, reaction obtains vanadium phosphate oxygen lithium presoma.
(3) the lithium-rich manganese-based layered lithium ion battery positive electrodes of 1g in (1) are weighed, vanadium phosphate oxygen lithium presoma is added to
In, by stirring 30min, ultrasound 30min, negative pressure impregnation 12h, vacuum pressure is 0.05-0.08MPa, drying, obtains vanadium phosphate
Oxygen lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor；
(4) the vanadyl phosphate lithium that will be obtained is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor in 70 DEG C of skies
12-24h, Muffle furnace calcining are dried in gas, Temperature Treatment is 300 DEG C, 4h, and 500 DEG C, 4h obtain 0.95g vanadyl phosphates lithium and be modified
Lithium-rich manganese-based layered lithium ion battery positive electrode, it is powdered, and chemical formula is [0.1Li2MnO3·0.9Li
Mn0.333Co0.333Ni0.333O2]·0.0009LiVOPO4。
Embodiment 2
A kind of vanadyl phosphate lithium of the invention is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, its
Comprise the following steps that：
(1) manganese acetate 0.03997mol, cobalt nitrate 0.02997mol, nickel nitrate 0.02997mol are dissolved in 100mL successively
In deionized water, the citric acid of 0.09mol and the lithium nitrate of 0.11mol are added, it is 7 to adjust pH value with ammoniacal liquor afterwards, in 80 DEG C
Under water bath condition, 4h is stirred, form precursor sol, 100 DEG C of insulation 36h in air.Muffle furnace is calcined, and Temperature Treatment is 450
DEG C, 5h, 900 DEG C, 12h.Lithium-rich manganese-based layered lithium ion battery positive electrode is obtained, it is powdered.
(2) ammonium vanadate for weighing 0.045mol is dissolved in 100mL deionized waters, under 70 DEG C of water bath conditions, stirs 2h, will
0.045mol lithium nitrates, finally add 0.045mol ammonium dihydrogen phosphates, and reaction obtains vanadium phosphate oxygen lithium colloidal sol.
(3) lithium-rich manganese-based layered lithium ion battery positive electrode is added in vanadium phosphate oxygen lithium colloidal sol, by stirring
30min, ultrasound 30min, negative pressure impregnation 12h, vacuum pressure is 0.05-0.08MPa, drying, obtains the modified richness of vanadium phosphate oxygen lithium
Li Meng basic units shape precursor of lithium ionic cell positive material；
(4) the vanadyl phosphate lithium that will be obtained is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor in 70 DEG C of skies
Dry 24h in gas, Muffle furnace calcining, Temperature Treatment is 600 DEG C, 5h, obtains 0.95g vanadyl phosphate lithiums and is modified lithium-rich manganese-based stratiform
Anode material for lithium-ion batteries, it is powdered, is [0.1Li with chemical formula2MnO3·0.9Li
Mn0.333Co0.333Ni0.333O2]·0.45LiVOPO4。
Embodiment 3
A kind of vanadyl phosphate lithium of the invention is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, its
Comprise the following steps that：
(1) manganese acetate 0.03997mol, cobalt nitrate 0.02997mol, nickel nitrate 0.02997mol are dissolved in 100mL successively
In deionized water, 0.18mol citric acids are added, add 0.11mol lithium nitrates, it is 8 to adjust pH value with ammoniacal liquor afterwards, in 80 DEG C of water
Under the conditions of bath, 4h is stirred, form precursor sol, 100 DEG C of insulation 24h in air.Muffle furnace calcine, Temperature Treatment be 450 DEG C,
5h, 900 DEG C, 12h.Lithium-rich manganese-based layered lithium ion battery positive electrode is obtained, it is powdered.
(2) citric acid for weighing 0.13365mol is dissolved in 100mL deionized waters, and 0.04455mol vanadic anhydrides are added
Enter, under 80 DEG C of water bath conditions, stir 2h, the lithium acetate of 0.0891mol is added, finally by the biphosphate of 0.0891mol
Ammonium is added, and reaction obtains vanadium phosphate oxygen lithium precursor solution.
(3) lithium-rich manganese-based layered lithium ion battery positive electrode in (1) is added in vanadium phosphate oxygen lithium precursor solution,
By stirring 30min, ultrasound 30min, negative pressure impregnation 6h, vacuum pressure is 0.05-0.08MPa, drying, obtains vanadium phosphate oxygen lithium
Be modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor；
(4) the vanadyl phosphate lithium that will be obtained is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor in 70 DEG C of skies
Dry 12h in gas, Muffle furnace calcining, Temperature Treatment is 600 DEG C, 5h, obtain vanadyl phosphate lithium be modified lithium-rich manganese-based Layered Lithium from
Sub- cell positive material, it is powdered, is [0.1Li with chemical formula2MnO3·0.9Li Mn0.333Co0.333Ni0.333O2]·
0.891LiVOPO4。
Embodiment 4
A kind of vanadyl phosphate lithium of the invention is modified the preparation method of lithium-rich manganese-based layered lithium ion battery time positive electrode,
It is comprised the following steps that：
(1) by 0.09333mol manganese nitrates, 0.0033mol cobalt nitrates, 0.0033mol nickel nitrates are dissolved in 150mL second successively
Glycol ether, 50 DEG C of water-baths form clear solution, and acetylacetone,2,4-pentanedione, the lithium nitrate of 0.19mol of 0.2mol are sequentially added afterwards,
Under water bath condition, 80 DEG C are warming up to, stirring, evaporation form precursor sol, 100-120 DEG C of insulation 36h in air.Muffle furnace
Calcining, Temperature Treatment is 450 DEG C, 5h, 900 DEG C, 12h.Lithium-rich manganese-based layered lithium ion battery positive electrode is obtained, it is powder
Shape.
(2) weigh 0.00001mol ammonium vanadate to be dissolved in 100mL deionized waters, under 80 DEG C of water bath conditions, stir
30min, instills the phosphoric acid after 0.00001mol dilutions, finally adds 0.00001mol lithium nitrates, and reaction obtains vanadyl phosphate
Lithium precursor solution.
(3) lithium-rich manganese-based layered lithium ion battery positive electrode in (1) is added in vanadium phosphate oxygen lithium solution, by stirring
30min, ultrasound 30min, negative pressure impregnation 6h are mixed, vacuum pressure is 0.05-0.08MPa, dried, obtain the modified richness of vanadium phosphate oxygen lithium
Li Meng basic units shape precursor of lithium ionic cell positive material；
(4) the vanadyl phosphate lithium that will be obtained is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor in 80 DEG C of skies
Dry 24h in gas, Muffle furnace calcining, Temperature Treatment is 600 DEG C, 5h, obtain vanadyl phosphate lithium be modified lithium-rich manganese-based Layered Lithium from
Sub- cell positive material, it is powdered, is [0.9Li with chemical formula2MnO3·0.1Li Mn0.333Co0.333Ni0.333O2]·
0.0001LiVOPO4。
Embodiment 5
A kind of vanadyl phosphate lithium of the invention is modified the preparation method of lithium-rich manganese-based layered cathode material, and specific steps are such as
Under：
(1) by 0.09333mol manganese acetates, 0.00333mol acetic acid is bored, and 0.00333mol nickel acetates are dissolved in 100mL successively
In deionized water, 50 DEG C of stirring in water bath form transparent aqueous solution；0.1mol sodium carbonate is dissolved in 50mL deionized waters and forms carbonic acid
Sodium water solution；The ammonium hydrogen carbonate of 0.1mol is dissolved in 50mL deionized waters and forms ammonium bicarbonate aqueous solution；By three kinds of solution three-phases simultaneously
Stream, coutroi velocity makes it be instilled simultaneously with identical flow velocity during the pH equipped with a small amount of ammoniacal liquor is 9 deionized water solution, while
Under 50 DEG C of water bath conditions, after being stirred vigorously 7h, precipitation 12h, filtering drying；The powder and the carbon of 0.095mol that will be filtrated to get
Sour lithium grinding, is placed in Muffle furnace, 900 DEG C of calcination 15h, obtains lithium-rich manganese-based layered lithium ion battery positive electrode, and it is powder
Last shape.
(2) weigh 0.0005mol ammonium vanadate to be dissolved in 100mL deionized waters, under 80 DEG C of water bath conditions, stir 30min,
The phosphoric acid after 0.0005mol dilutions is instilled, finally 0.0005mol lithium nitrates is added, reaction obtains vanadyl phosphate lithium presoma
Solution.
(3) lithium-rich manganese-based layered lithium ion battery positive electrode in (1) is added in vanadium phosphate oxygen lithium solution, by stirring
30min, ultrasound 30min, negative pressure impregnation 1h are mixed, vacuum pressure is 0.05-0.08MPa, dried, obtain the modified richness of vanadium phosphate oxygen lithium
Li Meng basic units shape precursor of lithium ionic cell positive material；
(4) the vanadyl phosphate lithium that will be obtained is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor in 80 DEG C of skies
Dry 24h in gas, Muffle furnace calcining, Temperature Treatment is 600 DEG C, 5h, obtain vanadyl phosphate lithium be modified lithium-rich manganese-based Layered Lithium from
Sub- cell positive material, it is powdered, is [0.9Li with chemical formula2MnO3·0.1Li Mn0.333Co0.333Ni0.333O2]·
0.05LiVOPO4。
Embodiment 6
A kind of vanadyl phosphate lithium of the invention is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, its
Comprise the following steps that：
(1) manganese acetate 0.09333mol, cobalt acetate 0.00333mol, nickel acetate 0.00333mol are dissolved in 100mL successively
In deionized water, 0.19mol lithium nitrates are added, add 0.2mol sucrose, under 80 DEG C of water bath conditions, stir 5h, form forerunner
Body colloidal sol, 100 DEG C of insulation 24h in air.Muffle furnace is calcined, and Temperature Treatment is 450 DEG C, 5h, 900 DEG C, 12h.Obtain rich lithium manganese
Basic unit's shape anode material for lithium-ion batteries, it is powdered.
(2) oxalic acid for weighing 0.0165mol is dissolved in 20mL deionized waters, and 0.00495mol vanadic anhydrides are added,
In under 70 DEG C of water bath conditions, 2h is stirred, 0.0099mol lithium nitrates finally added 0.0099mol ammonium dihydrogen phosphates, reaction
Obtain vanadium phosphate oxygen lithium solution.
(3) lithium-rich manganese-based layered lithium ion battery positive electrode in (1) is added in vanadium phosphate oxygen lithium solution, by stirring
30min, ultrasound 30min, negative pressure impregnation 1h are mixed, vacuum pressure is 0.05-0.08MPa, dried, obtain the modified richness of vanadium phosphate oxygen lithium
Li Meng basic units shape precursor of lithium ionic cell positive material；
(4) the vanadyl phosphate lithium that will be obtained is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor in 70 DEG C of skies
12h, Muffle furnace calcining are dried in gas, Temperature Treatment is 300 DEG C, 4h, and 500 DEG C, 4h obtain the modified richness of 0.95g vanadyl phosphates lithium
Li Meng basic units shape anode material for lithium-ion batteries, it is powdered, is [0.9Li with chemical formula2MnO3·0.1Li
Mn0.333Co0.333Ni0.333O2]·0.099LiVOPO4。
Embodiment 7
A kind of vanadyl phosphate lithium of the invention is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, its
Comprise the following steps that：
(1) by manganese acetate 0.0533mol, cobalt acetate 0.0233mol, nickel acetate 0.0233mol be dissolved in successively 100mL go from
In sub- water, 0.07mol citric acids are added, add 0.13mol lithium nitrates, it is 8 to adjust pH value with ammoniacal liquor afterwards, in 80 DEG C of water-bath bars
Under part, 5h is stirred, form precursor sol, 100 DEG C of insulation 36h in air.Muffle furnace calcine, Temperature Treatment be 450 DEG C, 5h,
900℃、12h.Manganese Quito unit substrate positive electrode is obtained, it is powdered.
(2) oxalic acid for weighing 0.0105mol is dissolved in 100mL deionized waters, and 0.0035mol vanadic anhydrides are added,
In under 70 DEG C of water bath conditions, 2h is stirred, 0.007mol lithium nitrates finally add 0.007mol ammonium dihydrogen phosphates, reacted
To vanadium phosphate oxygen lithium solution.
(3) the lithium-rich manganese-based layered lithium ion battery positive electrode that will be obtained in (1), is added to vanadium phosphate oxygen lithium solution
In, by stirring 30min, ultrasound 30min, negative pressure impregnation 6h, vacuum pressure is 0.05-0.08MPa, drying, obtains vanadium phosphate
Oxygen lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor；
(4) the vanadyl phosphate lithium that will be obtained is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor in 70 DEG C of skies
Dry 24h in gas, Muffle furnace calcining, Temperature Treatment is 300 DEG C, 4h, 500 DEG C, 4h, obtain vanadyl phosphate lithium be modified it is lithium-rich manganese-based
Layered lithium ion battery positive electrode, it is powdered, is [0.3Li with chemical formula2MnO3·0.7Li
Mn0.333Co0.333Ni0.333O2]·0.07LiVOPO4。
Embodiment 8
A kind of vanadium phosphate oxygen lithium of the invention is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, tool
Body step is as follows：
(1) with the lithium-rich manganese-based layered lithium ion battery positive electrode powder of step (1) preparation in embodiment 7 the step of
It is identical.
(2) oxalic acid for weighing 0.0105mol is dissolved in 100mL deionized waters, and 0.0035mol vanadic anhydrides are added,
In under 70 DEG C of water bath conditions, 2h is stirred, 0.007mol lithium nitrates finally add 0.007mol ammonium dihydrogen phosphates, stirring is extremely
Solvent all evaporates, and reaction obtains vanadium phosphate oxygen lithium presoma green powder.
(3) the vanadium phosphate oxygen lithium presoma that will be obtained in lithium-rich manganese-based layered lithium ion battery positive electrode in (1) and (2)
Green powder mixed grinding.
(4) the vanadyl phosphate lithium that will be obtained is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor, Muffle furnace
Middle calcining, Temperature Treatment is 300 DEG C, 4h, and 500 DEG C, 4h obtain vanadyl phosphate lithium and be modified lithium-rich manganese-based layered lithium ion battery just
Pole material, it is powdered, is [0.3Li with chemical formula2MnO3·0.7Li Mn0.333Co0.333Ni0.333O2]·
0.07LiVOPO4。
Be modified lithium-rich manganese-based layered lithium ion battery positive electrode in the present invention to the vanadyl phosphate lithium of all embodiments
Chemical property is detected.
With reference to accompanying drawing, the vanadyl phosphate lithium prepared with the explanation of embodiment 7 is modified lithium-rich manganese-based layered lithium ion battery positive pole
The chemical property of material, its characterization result is as follows：
Fig. 1 be embodiment 7 prepare vanadyl phosphate lithium be modified lithium-rich manganese-based layered cathode active material ESEM shine
Piece.As seen from the figure, a kind of the be modified particle diameter of lithium-rich manganese-based layered cathode active material of finally prepd vanadyl phosphate lithium exists
200nm or so.
Fig. 2 is that vanadyl phosphate lithium prepared by embodiment 7 is modified lithium-rich manganese-based layered cathode active material in the case of 0.1C
Preceding 9 charging and discharging curve figures, abscissa is the specific capacity (sepecific capacity) of material, and unit is mAh/g, ordinate
It is voltage (voltage) that unit is V；In figure, in rising trend represents the charge data for circulating 1,4,7,9 times respectively, under being in
The expression respectively of drop trend circulates the discharge data of 1,4,7,9 times.As seen from the figure, the anode active material of lithium ion battery is first
Discharge platform is carried out in more than 2.8V with discharge and recharge, and discharge platform decay is very slow, almost unattenuated, first discharge specific capacity
It is 253mAh/g, after discharge and recharge 9 times, specific discharge capacity still has 235mAh/g.And from 2 to 9 process, specific discharge capacity almost without
Decay.
Present example 7 improves lithium-rich manganese-based layer using the characteristic of the electrochemical reaction platform stable of vanadyl phosphate lithium
The electrochemical stability and high rate performance of shape anode material for lithium-ion batteries, obtain a kind of modified electrode material of stable circulation.
Vanadyl phosphate lithium prepared by embodiment 1-6 is modified lithium-rich manganese-based layered lithium ion battery positive electrode, its electrochemistry
Performance quite, equally shows good rate capability, the advantage of stable circulation with embodiment 7.
Fig. 3 be embodiment 7 prepare vanadyl phosphate lithium be modified lithium-rich manganese-based layered cathode active material ESEM shine
Piece figure.As seen from the figure, a kind of finally prepd vanadyl phosphate lithium is modified the particle diameter of lithium-rich manganese-based layered cathode active material
200nm or so.
Fig. 4 is that vanadyl phosphate lithium prepared by embodiment 8 is modified lithium-rich manganese-based layered cathode active material in the case of 0.1C
Preceding 9 charging and discharging curve figures.Its abscissa is the specific capacity (sepecific capacity) of material, and unit is mAh/g, indulges and sits
Voltage (voltage) is designated as, unit is V；In figure, in rising trend represents the charge data for circulating 1,4,7,9 times respectively, is in
The expression respectively of downward trend circulates the discharge data of 1,4,7,9 times.As seen from the figure, the anode active material of lithium ion battery is first
Secondary discharge platform is carried out in more than 2.8V with discharge and recharge, and discharge platform decay is very slow, and almost unattenuated, discharge specific volume first
It is 252mAh/g to measure, and after discharge and recharge 9 times, specific discharge capacity still has 245mAh/g.And from 2 to 9 process, specific discharge capacity is almost
It is undamped.
Present example 8 improves lithium-rich manganese-based layer using the characteristic of the electrochemical reaction platform stable of vanadyl phosphate lithium
The electrochemical stability and high rate performance of shape anode material for lithium-ion batteries, obtain a kind of modified electrode material of stable circulation.
Obviously, the present invention is modified by vanadyl phosphate lithium to lithium-rich manganese-based layered lithium ion battery positive electrode, can
To alleviate its platform decay and special capacity fade problem in discharge process, its cyclical stability is improved to a certain extent.
Although the present invention is described in detail with a general description of the specific embodiments in this specification,
But on the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.
Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed model
Enclose.
Claims (10)
1. vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that its chemical general formula
xLi2MnO3·(1-x)LiMO2·yLiVOPO4, wherein, 0.1≤x≤0.9, M is Mn, Co and Ni, and the percentage that y accounts for x is
0.1-99%.
2. the vanadyl phosphate lithium described in claim 1 is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that
Including following raw material components：Manganese raw material, nickel raw material, cobalt raw material, lithium salts, phosphorus source, vanadium source, complexing agent and reducing agent.
3. vanadyl phosphate lithium according to claim 2 is modified lithium-rich manganese-based layered lithium ion battery positive electrode, its feature
It is that the manganese raw material is manganese metal, Mn oxide, inorganic salts containing manganese, organic salt containing manganese or alkoxide containing manganese；The nickel raw material is
Metallic nickel, nickel oxide, nickeliferous inorganic salts, nickeliferous organic salt or nickeliferous alkoxide；The cobalt raw material be metallic cobalt, cobalt/cobalt oxide,
Inorganic salts containing cobalt, organic salt containing cobalt or alkoxide containing cobalt；The lithium salts is oxidate for lithium, inorganic salts containing lithium, organic salt containing lithium or contains
Lithium alkoxide；Phosphorus source is phosphorous organic phosphate or phosphorous organophosphorus ester；The vanadium source is barium oxide, organic vanadic acid
Salt, organic vanadium acid esters；The complexing agent be alcamines complexing agent, hydroxycarboxylic acid complexing agent, organic phosphate complexing agent or
Polyacrylic complexing agent；The reducing agent is organic acid reducing agent, inorganic acids reducing agent or alcohols reducing agent.
4. vanadyl phosphate lithium according to claim 3 is modified lithium-rich manganese-based layered lithium ion battery positive electrode, its feature
It is, in the lithium salts, manganese raw material, nickel raw material and cobalt raw material, Li+、Mn2+、Ni2+With Co2+Mol ratio be (1.1~1.9)：
(0.3997~0.9333)：(0.2997~0.0333)：(0.2997~0.0333).
5. the vanadyl phosphate lithium described in claim 1 or 2 is modified the preparation side of lithium-rich manganese-based layered lithium ion battery positive electrode
Method, it is characterised in that comprise the following steps：
Step 1, prepares lithium-rich manganese-based layered lithium ion battery positive electrode：Manganese raw material, nickel raw material, cobalt raw material are dissolved in liquid successively
In body solvent, complexing agent, lithium salts are added, heating water bath, stirring reaction obtain precursor sol, and 100 DEG C are incubated 24-36h,
It is finally thermally treated to obtain lithium-rich manganese-based layered lithium ion battery positive electrode；
Step 2, prepares vanadyl phosphate lithium solution：Vanadium source and reducing agent are dissolved in liquid flux, lithium salts, phosphorus source, water is added
Bath heating, stirring reaction, form colloidal sol, obtain vanadyl phosphate lithium solution；
Step 3, prepares vanadyl phosphate lithium and is modified lithium-rich manganese-based layered lithium ion battery positive pole using collosol and gel liquid phase cladding process
Material：By in lithium-rich manganese-based layered cathode material addition vanadyl phosphate lithium solution, agitated, ultrasonic, negative pressure impregnation obtains phosphoric acid
Vanadyl lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor, finally by the modified richness lithium manganese of the vanadyl phosphate lithium
Basic unit's shape precursor of lithium ionic cell positive material dries 12-24h for 70 DEG C in atmosphere, then is heat-treated, and obtains final product.
6. vanadyl phosphate lithium according to claim 5 is modified the preparation side of lithium-rich manganese-based layered lithium ion battery positive electrode
Method, it is characterised in that in step 1, the temperature of the heating water bath is 50-90 DEG C；The time of the stirring reaction is 3-5h；Institute
State heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, successively under the conditions of 450 DEG C calcine 5h, 900 DEG C
Under the conditions of calcine 12h.
7. vanadyl phosphate lithium according to claim 5 is modified the preparation side of lithium-rich manganese-based layered lithium ion battery positive electrode
Method, it is characterised in that in step 2, the temperature of the heating water bath is 70-80 DEG C, and the time of the stirring reaction is 0.5-2h.
8. vanadyl phosphate lithium according to claim 5 is modified the preparation side of lithium-rich manganese-based layered lithium ion battery positive electrode
Method, it is characterised in that in step 3, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, exist successively
4h is calcined under the conditions of 300 DEG C, 4h is calcined under the conditions of 500 DEG C.
9. the vanadyl phosphate lithium described in claim 1 or 2 is modified the preparation side of lithium-rich manganese-based layered lithium ion battery positive electrode
Method, it is characterised in that comprise the following steps：
Step 1, prepares lithium-rich manganese-based layered lithium ion battery positive electrode：Manganese raw material, nickel raw material, cobalt raw material are dissolved in liquid successively
In body solvent, complexing agent, lithium salts are added, heating water bath, stirring reaction obtain precursor sol, and 100 DEG C are incubated 24-36h,
It is finally thermally treated to obtain lithium-rich manganese-based layered lithium ion battery positive electrode；
Step 2, prepares vanadyl phosphate lithium presoma：Vanadium source and reducing agent are dissolved in liquid flux, lithium salts, phosphorus source is added,
Heating water bath, stirring reaction, form colloidal sol, and drying obtains vanadyl phosphate lithium precursor powder.
Step 3, prepares vanadyl phosphate lithium and is modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based stratiform
Anode material for lithium-ion batteries mixes with the vanadyl phosphate lithium precursor powder, and grinds uniform, after heat treatment, obtains final product.
10. vanadyl phosphate lithium according to claim 9 is modified the preparation of lithium-rich manganese-based layered lithium ion battery positive electrode
Method, it is characterised in that in step 2, the temperature of the drying is 50-100 DEG C；In step 3, the time of the grinding is 2-
5h。
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