CN106340639B - A kind of hud typed iron manganese phosphate for lithium composite positive pole and preparation method thereof of lithium iron phosphate/carbon cladding - Google Patents
A kind of hud typed iron manganese phosphate for lithium composite positive pole and preparation method thereof of lithium iron phosphate/carbon cladding Download PDFInfo
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- CN106340639B CN106340639B CN201610969290.XA CN201610969290A CN106340639B CN 106340639 B CN106340639 B CN 106340639B CN 201610969290 A CN201610969290 A CN 201610969290A CN 106340639 B CN106340639 B CN 106340639B
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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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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a kind of hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, and composition general formula is LiMnxFe1‑xPO4/LiMnyFe1‑yPO4/LiFePO4/ C, wherein the composition general formula of nuclear material are as follows: LiMnxFe1‑xPO4, the composition general formula of Shell Materials is LiMnyFe1‑yPO4, the composition general formula of coating layer material is LiFePO4/ C, also, 0.8≤x≤0.9,0.2≤y≤0.4, meanwhile, weight percent shared by nuclear material is 60 ~ 80%, weight percent shared by Shell Materials is 15 ~ 30%, and weight percent shared by LiFePO4 is 3 ~ 7% in coating layer material, and weight percent shared by carbon is 2 ~ 3% in coating layer material.The present invention combines to obtain hud typed iron manganese phosphate lithium particle with hydro-thermal method using coprecipitation, then carries out hydro-thermal reaction after mixing with lithium source, source of iron, phosphorus source, carbon source and obtain target product.Using the rule of product particle spherical morphology made from the method for the present invention, and the dissolution of manganese in positive electrode is dramatically reduced, the cycle performance of battery is improved significantly.
Description
Technical field
The invention belongs to technical field of new energy material preparation, the hud typed phosphorus of specifically a kind of lithium iron phosphate/carbon cladding
Sour manganese iron lithium composite positive pole and preparation method thereof.
Background technique
Increasingly depleted with petroleum resources, energy problem has become human social strategy and has to solve
Important topic certainly.In recent years, operating voltage was high, energy density is big, has extended cycle life, memoryless effect because having for lithium ion battery
Answer, be small in size, is light-weight, non-environmental-pollution the advantages that, obtain faster development, wherein positive electrode is lithium ion battery
One of four important components, chemical property and security performance to lithium ion battery have prayed vital effect,
And its cost is also close to the nearly half of entire lithium ion battery totle drilling cost.Therefore the research and development of positive electrode are always people's research
Emphasis.
Phosphate of olivine type base anode material LiMPO4(M=Fe, Mn, Co and Ni etc.) has relative to layered cathode material
There are stable structure, cost-effectiveness and environmental-friendly and largely paid close attention to.Wherein olivine-type LiFePO4Due to the stabilization of structure
Property is widely used as the positive electrode of lithium ion battery, however lower (the 3.5Vvs. Li of its voltage+/ Li), make energy density not
Height limits its application in high-energy device.And olivine-type LiMnPO4Due to higher voltage (4.0V vs.
Li+/ Li), and theoretical energy density ratio LiFePO4It is big by 20%, and theoretical specific capacity and LiFePO4Close (~ 170mAhg-1), it inhales
A large amount of concern is drawn.However, its electronic conductivity ratio LiFePO4It is lower, it is considered to be insulator, make its discharge capacity it is low,
High rate performance is poor, and dissolution can occur in cyclic process and keep capacity retention ratio poor and Mn by Mn3+The Jahn- of generation
Teller distortion, limits LiMnPO4Application.
LiMn can be formed by largely studying discovery Mn and Fe1-xFexPO4Solid solution has similar LiFePO4Olive
Olive stone structure.Stabilization electrochemical window of its operating voltage in 3.5 ~ 4.1V, suitable for traditional electrolyte liquid system.It can protect
The high rate performance and cycle performance of material are improved while demonstrate,proving specific capacity.General higher Fe content can reduce the dissolution of Mn,
To improve the cycle performance of material, make LiMn1-xFexPO4As the most promising positive electrode of high performance lithium ion battery it
One.
In order to improve LiMn1-xFexPO4The performance of positive electrode, it is necessary to which a major issue of solution is exactly the molten of Mn
Solution.LiMn is solved at present1-xFexPO4The method of positive electrode dissolution has positive electrode surface cladding, ion doping, changes electrolysis
Liquid etc..
In view of the status of the prior art, the present inventor deeply widely grind for lithium iron manganese phosphate anode material
Study carefully, the hud typed iron manganese phosphate for lithium composite positive pole that discovery lithium iron phosphate/carbon coats, high specific capacity can kept
Meanwhile the dissolution of Mn is reduced, significantly improve the cycle performance of material.
Summary of the invention
It is an object of the invention to overcome defect of the existing technology, provide that a kind of safety is good, thermal stability is high, energy
Substantially reduce Mn dissolution, the hud typed iron manganese phosphate for lithium for the lithium iron phosphate/carbon cladding for improving the features such as cycle performance of material is answered
Close positive electrode and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, the composite positive pole group
It is LiMn at general formulaxFe1-xPO4/LiMnyFe1-yPO4/LiFePO4/ C, wherein the composition general formula of nuclear material are as follows: LiMnxFe1- xPO4, the composition general formula of Shell Materials is LiMnyFe1-yPO4, the composition general formula of coating layer material is LiFePO4/ C, also, 0.8
≤ x≤0.9,0.2≤y≤0.4, meanwhile, weight percent shared by nuclear material is 60 ~ 80%, weight percent shared by Shell Materials
It is 15 ~ 30%, weight percent shared by LiFePO4 is 3 ~ 7% in coating layer material, weight percent shared by carbon in coating layer material
Number is 2 ~ 3%.
It is another object of the present invention to provide a kind of hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding is compound just
The preparation method of pole material, the described method comprises the following steps:
(1) crystallinity MnxFe1-xPO4Anhydrous compound: it is that x:1-x weighs manganese source, source of iron by the molar ratio of Mn:Fe, mixes
In ethanol, H is added while stirring3PO4Solution obtains the precipitating of celadon after reacting 4 ~ 7h at 30 DEG C, product is carried out
It filters, washing under protective atmosphere, in 650 ~ 800 DEG C of 10 ~ 20h of roasting temperature, obtains after 80 DEG C of vacuum drying for 24 hours
Crystallinity MnxFe1-xPO4Anhydrous compound；
(2) hud typed iron manganese phosphate for lithium: by step (1) crystallinity MnxFe1-xPO4Anhydrous compound and manganese source, source of iron, phosphorus
Source and lithium source stoichiometrically mix in deionized water, stir evenly and are transferred in hydrothermal reaction kettle after forming suspension,
8 ~ 15h is reacted in 150 ~ 200 DEG C of baking oven, product is filtered, washed, after drying for 24 hours at 80 DEG C, in protective atmosphere
Under, in 650 ~ 800 DEG C of 5 ~ 10h of roasting temperature, obtain the hud typed iron manganese phosphate lithium particle of crystallinity；
(3) the hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding: the hud typed iron manganese phosphate lithium particle of step (2) is added
Enter into a certain amount of lithium hydroxide aqueous solution, the source of iron and phosphorus with lithium hydroxide equimolar amounts are instilled while being dispersed with stirring
Source adds carbon source, quickly stir 10 ~ 60min after, be transferred in hydrothermal reaction kettle, in 150 ~ 200 DEG C of baking oven react 5 ~
Product is filtered, is washed by 8h, after being dried for 24 hours at 80 DEG C, under protective atmosphere, in 650 ~ 800 DEG C of roasting temperatures 3 ~
8h obtains the hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding；
The stoichiometric ratio of above-mentioned each substance presses general formula LiMnxFe1-xPO4/LiMnyFe1-yPO4/LiFePO4/ C determines,
Wherein, 0.8≤x≤0.9,0.2≤y≤0.4, LiMnxFe1-xPO4Shared weight percent is 60 ~ 80%, LiMnyFe1-yPO4Institute
Accounting for weight percent is 15 ~ 30%, LiFePO4Weight percent shared by LiFePO4 is 3 ~ 7%, LiFePO in/C4In/C shared by carbon
Weight percent is 2 ~ 3%.
Preferably, the manganese source is one of manganese nitrate, manganese sulfate, manganese chloride, manganese carbonate or two kinds of combinations.
Preferably, the source of iron is ferrous oxalate, ferric nitrate, any one or two kinds of combinations in ferrous sulfate.
Preferably, phosphorus source is ammonium dihydrogen phosphate.
Preferably, the lithium source is one of lithium carbonate, lithium hydroxide or two kinds of combinations.
Preferably, the carbon source is one of sucrose, glucose, citric acid, PEG20000 or two kinds of combinations.
Preferably, the protective atmosphere is nitrogen, in argon gas, nitrogen-hydrogen (95:5), argon gas-hydrogen (95:5)
The combination of any one or two kinds.
Beneficial effects of the present invention: the present invention is prepared for ferric phosphate using the method that coprecipitation and hydro-thermal method combine
Lithium/carbon-coated hud typed iron manganese phosphate for lithium composite positive pole.In core-shell structure, the content of Mn is high in nuclear material, provides material
Expect higher voltage and high capacity, and the content of Mn is less in Shell Materials, reduces the dissolution of Mn in material, clad is by phosphorus
Sour iron lithium/carbon composition, further prevents contact of the core-shell material with electrolyte, reduces the dissolution of Mn, while carbon prevents
Reunion between particle improves the conductivity of material.The hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding of the present invention is compound
Positive electrode specific capacity with higher, and cycle performance is excellent；Preparation method of the present invention is simple, safe, easily operated.
Detailed description of the invention
The structural representation of the iron manganese phosphate for lithium composite positive pole for the lithium iron phosphate/carbon cladding that Fig. 1 embodiment 1 is prepared
Figure, wherein 1 is the core of richness Mn, 2 be the shell of richness Fe, and 3 be LiFePO4/ C clad；
Fig. 2 is the iron manganese phosphate for lithium composite positive pole section for the lithium iron phosphate/carbon cladding that embodiment 1 is prepared
SEM picture；
Fig. 3 is the iron manganese phosphate for lithium composite positive pole group for the lithium iron phosphate/carbon cladding that the embodiment of the present invention 1 is prepared
The cyclic curve of the battery of dress；
Fig. 4 is the cyclic curve of the battery of the carbon-coated non-hud typed lithium iron manganese phosphate anode material assembling of comparative example.
Specific embodiment
Present invention is further described in detail in the following with reference to the drawings and specific embodiments.
A kind of composition general formula of the hud typed iron manganese phosphate for lithium composite positive pole of present invention lithium iron phosphate/carbon cladding is
LiMnxFe1-xPO4/LiMnyFe1-yPO4/LiFePO4/ C, wherein the composition general formula of nuclear material are as follows: LiMnxFe1-xPO4, shell material
The composition general formula of material is LiMnyFe1-yPO4, the composition general formula of coating layer material is LiFePO4/ C, also, 0.8≤x≤0.9,
0.2≤y≤0.4, meanwhile, weight percent shared by nuclear material is 60 ~ 80%, and weight percent shared by Shell Materials is 15 ~ 30%,
Weight percent shared by LiFePO4 is 3 ~ 7% in coating layer material, and weight percent shared by carbon is 2 ~ 3% in coating layer material,
The stoichiometric ratio of each substance is according to the x in general formula in the embodiment of the present invention, and the weight ratio of y and each component is calculated
's.
Embodiment 1
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, forms general formula are as follows:
LiMn0.9Fe0.1PO4/LiMn0.2Fe0.8PO4/LiFePO4/ C, wherein weight percent shared by nuclear material is 80%, Shell Materials institute
Accounting for weight percent is 15%, and weight percent shared by LiFePO4 is 3% in coating layer material, weight shared by carbon in coating layer material
Measuring percentage is 2%.
1, crystallinity Mn is prepared0.9Fe0.1PO4Anhydrous compound: the ferrous oxalate of 9mol manganese nitrate, 1mol are blended in second
In alcohol, 1molH is added in stirring while3PO4Solution obtains the precipitating of celadon after reacting 4h at 30 DEG C, product is taken out
Filter, washing, obtain amorphous Mn0.9Fe0.1PO4Hydrate, after 80 DEG C of vacuum drying for 24 hours, then in a nitrogen atmosphere, by its
10h is roasted at 800 DEG C, obtains crystallinity Mn0.9Fe0.1PO4Anhydrous compound；
2, hud typed iron manganese phosphate for lithium is prepared: by above-mentioned crystallinity Mn0.9Fe0.1PO4Anhydrous compound and 0.037mol nitre
In deionized water, stirring is equal for sour manganese, 0.149mol ferrous oxalate, 0.19mol ammonium dihydrogen phosphate and the mixing of 0.59mol lithium carbonate
It is transferred in hydrothermal reaction kettle after even formation suspension, puts it into 150 DEG C of baking oven and react 15h, obtained product carries out
It filters, washing, after drying for 24 hours at 80 DEG C, then in a nitrogen atmosphere, roasts 5h at 800 DEG C, obtain the hud typed phosphoric acid of crystallinity
Manganese iron lithium particle；
3, it prepares the hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding: above-mentioned hud typed iron manganese phosphate lithium particle is added
Enter into 0.037mol lithium hydroxide aqueous solution, 0.037mol ferrous oxalate and 0.037mol phosphoric acid are instilled while being dispersed with stirring
Ammonium dihydrogen adds 19.6g sucrose, after quickly stirring 60min, is transferred in hydrothermal reaction kettle, is put into 150 DEG C of baking oven
8h is reacted, product is filtered, is washed, after being dried for 24 hours at 80 DEG C, then in a nitrogen atmosphere, 8h is roasted at 650 DEG C, obtains
The hud typed iron manganese phosphate lithium particle coated to lithium iron phosphate/carbon.
The composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity for measuring battery is
150mAh/g, first charge-discharge efficiency 94.5%, capacity retention ratio is 98.2% after recycling 100 weeks.
The structural representation of the iron manganese phosphate for lithium composite positive pole for the lithium iron phosphate/carbon cladding that Fig. 1 embodiment 1 is prepared
Figure, wherein 1 is the core of richness Mn, 2 be the shell of richness Fe, and 3 be LiFePO4/ C clad；Fig. 2 is what embodiment 1 was prepared
The SEM picture of the iron manganese phosphate for lithium composite positive pole section of lithium iron phosphate/carbon cladding；Fig. 3 is that the embodiment of the present invention 1 is prepared into
The cyclic curve of the battery of the iron manganese phosphate for lithium composite positive pole assembling of the lithium iron phosphate/carbon cladding arrived.
Comparative example
Carbon-coated non-hud typed lithium iron manganese phosphate anode material forms general formula are as follows: LiMn0.9Fe0.1PO4/ C, wherein
Iron manganese phosphate for lithium accounts for 95%, and carbon coating layer accounts for 5%.
9mol manganese nitrate, 1mol ferrous oxalate, 10mol ammonium dihydrogen phosphate and 5mol lithium carbonate mix in deionized water,
413g sucrose is added, stirs evenly and is transferred in hydrothermal reaction kettle after forming suspension, is put it into anti-in 150 DEG C of baking oven
15h is answered, obtained product is filtered, is washed, after drying for 24 hours at 80 DEG C, then in a nitrogen atmosphere, 5h is roasted at 800 DEG C,
Obtain carbon-coated non-hud typed lithium iron manganese phosphate anode material.
Fig. 4 is the cyclic curve of the battery of the carbon-coated non-hud typed lithium iron manganese phosphate anode material assembling of comparative example.
Embodiment 2
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, forms general formula are as follows:
LiMn0.85Fe0.15PO4/LiMn0.3Fe0.7PO4/LiFePO4/ C, wherein weight percent shared by nuclear material is 70%, Shell Materials
Shared weight percent is 20%, and weight percent shared by LiFePO4 is 7% in coating layer material, in coating layer material shared by carbon
Weight percent is 3%.
1, crystallinity Mn is prepared0.85Fe0.15PO4Anhydrous compound: the ferric nitrate of 8.5mol manganese sulfate, 1.5mol are mixed
In ethanol, 1molH is added while stirring3PO4Solution, at 30 DEG C react 7h after obtain the precipitating of celadon, by product into
Row is filtered, is washed, and obtains amorphous Mn0.85Fe0.15PO4Hydrate, after 80 DEG C of vacuum drying for 24 hours, then under an argon atmosphere,
It is roasted into 20h at 700 DEG C, obtains crystallinity Mn0.85Fe0.15PO4Anhydrous compound；
2, hud typed iron manganese phosphate for lithium is prepared: by above-mentioned crystallinity Mn0.85Fe0.15PO4Anhydrous compound and 0.085mol sulphur
In deionized water, stirring is equal for sour manganese, 0.199mol ferric nitrate, 0.28mol ammonium dihydrogen phosphate and the mixing of 1.28mol lithium hydroxide
It is transferred in hydrothermal reaction kettle after even formation suspension, puts it into 200 DEG C of baking oven and react 8h, obtained product is taken out
Filter, washing, after drying for 24 hours at 80 DEG C, then under an argon atmosphere, roast 10h at 700 DEG C, obtain the hud typed phosphoric acid of crystallinity
Manganese iron lithium particle；
3, it prepares the hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding: above-mentioned hud typed iron manganese phosphate lithium particle is added
Enter into 0.10mol lithium hydroxide aqueous solution, 0.10mol ferric nitrate and 0.10mol biphosphate are instilled while being dispersed with stirring
Ammonium adds 33.6g glucose, after quickly stirring 10min, is transferred in hydrothermal reaction kettle, is put into 200 DEG C of baking oven anti-
5h is answered, product is filtered, is washed, after being dried for 24 hours at 80 DEG C, then under an argon atmosphere, 3h is roasted at 800 DEG C, obtains
The hud typed iron manganese phosphate lithium particle of lithium iron phosphate/carbon cladding.
The composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity for measuring battery is
152 mAh/g, first charge-discharge efficiency 95.5%, capacity retention ratio is 97.8% after recycling 100 weeks.
Embodiment 3
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, forms general formula are as follows:
LiMn0.8Fe0.2PO4/LiMn0.4Fe0.6PO4/LiFePO4/ C, wherein weight percent shared by nuclear material is 60%, Shell Materials institute
Accounting for weight percent is 30%, and weight percent shared by LiFePO4 is 7% in coating layer material, weight shared by carbon in coating layer material
Measuring percentage is 3%.
1, crystallinity Mn is prepared0.8Fe0.2PO4Anhydrous compound: the ferric nitrate of 8.0mol manganese sulfate, 2.0mol are blended in
In ethyl alcohol, 1molH is added in stirring while3PO4Solution obtains the precipitating of celadon after reacting 6h at 30 DEG C, product is carried out
It filters, washing, obtains amorphous Mn0.8Fe0.2PO4Hydrate, after 80 DEG C of vacuum drying for 24 hours, then at argon gas-hydrogen (95:5)
Under atmosphere, it is roasted into 15h at 650 DEG C, obtains crystallinity Mn0.8Fe0.2PO4Anhydrous compound；
2, hud typed iron manganese phosphate for lithium is prepared: by above-mentioned crystallinity Mn0.8Fe0.2PO4Anhydrous compound and 0.20mol chlorination
Manganese, 0.299mol ferrous sulfate, 0.5mol ammonium dihydrogen phosphate and the mixing of 1.5mol lithium hydroxide in deionized water, stir evenly
It is transferred in hydrothermal reaction kettle after forming suspension, puts it into 170 DEG C of baking oven and react 10h, obtained product is taken out
Filter, washing, after drying for 24 hours at 80 DEG C, then under argon gas-hydrogen (95:5) atmosphere, roast 7h at 650 DEG C, obtain crystallinity
Hud typed iron manganese phosphate lithium particle；
3, it prepares the hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding: above-mentioned hud typed iron manganese phosphate lithium particle is added
Enter into 0.116mol lithium hydroxide aqueous solution, 0.116mol ferrous sulfate and 0.116mol phosphoric acid are instilled while being dispersed with stirring
Ammonium dihydrogen adds 39.3g citric acid, after quickly stirring 30min, is transferred in hydrothermal reaction kettle, is put into 180 DEG C of baking oven
Middle reaction 7h, product is filtered, is washed, after drying for 24 hours at 80 DEG C, then under argon gas-hydrogen (95:5) atmosphere, in 700
5h is roasted at DEG C, obtains the hud typed iron manganese phosphate lithium particle of lithium iron phosphate/carbon cladding.
The composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity for measuring battery is
149 mAh/g, first charge-discharge efficiency 95.9%, capacity retention ratio is 97.1% after recycling 100 weeks.
Embodiment 4
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, forms general formula are as follows:
LiMn0.8Fe0.2PO4/LiMn0.25Fe0.75PO4/LiFePO4/ C, wherein weight percent shared by nuclear material is 75%, Shell Materials
Shared weight percent is 17.5%, and weight percent shared by LiFePO4 is 5% in coating layer material, carbon institute in coating layer material
Accounting for weight percent is 2.5%.
1, crystallinity Mn is prepared0.8Fe0.2PO4Anhydrous compound: the ferric nitrate of 8.0mol manganese carbonate, 2.0mol are blended in
In ethyl alcohol, 1molH is added in stirring while3PO4Solution obtains the precipitating of celadon after reacting 5h at 30 DEG C, product is carried out
It filters, washing, obtains amorphous Mn0.8Fe0.2PO4Hydrate, after 80 DEG C of vacuum drying for 24 hours, then at nitrogen-hydrogen (95:5)
Under atmosphere, it is roasted into 20h at 650 DEG C, obtains crystallinity Mn0.8Fe0.2PO4Anhydrous compound；
2, hud typed iron manganese phosphate for lithium is prepared: by above-mentioned crystallinity Mn0.8Fe0.2PO4Anhydrous compound and 0.058mol carbon
Sour manganese, 0.174mol ferric nitrate, 0.23mol ammonium dihydrogen phosphate and the mixing of 0.62mol lithium carbonate in deionized water, stir evenly
It is transferred in hydrothermal reaction kettle after forming suspension, puts it into 170 DEG C of baking oven and react 9h, obtained product is taken out
Filter, washing, after drying for 24 hours at 80 DEG C, then under nitrogen-hydrogen (95:5) atmosphere, roast 5h at 650 DEG C, obtain crystallinity
Hud typed iron manganese phosphate lithium particle；
3, it prepares the hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding: above-mentioned hud typed iron manganese phosphate lithium particle is added
Enter into 0.066mol lithium hydroxide aqueous solution, 0.066mol ferric nitrate and 0.066mol di(2-ethylhexyl)phosphate are instilled while being dispersed with stirring
Hydrogen ammonium, adds 26.2gPEG20000, after quickly stirring 50min, is transferred in hydrothermal reaction kettle, is put into 170 DEG C of baking oven
Middle reaction 6h, product is filtered, is washed, after drying for 24 hours at 80 DEG C, then under nitrogen-hydrogen (95:5) atmosphere, in 750
4h is roasted at DEG C, obtains the hud typed iron manganese phosphate lithium particle of lithium iron phosphate/carbon cladding.
The composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity for measuring battery is
147mAh/g, first charge-discharge efficiency 94.9%, capacity retention ratio is 97.5% after recycling 100 weeks.
Embodiment 5
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, forms general formula are as follows:
LiMn0.87Fe0.13PO4/LiMn0.23Fe0.77PO4/LiFePO4/ C, wherein weight percent shared by nuclear material is 75%, shell material
Expect that shared weight percent is 18%, weight percent shared by LiFePO4 is 4% in coating layer material, carbon institute in coating layer material
Accounting for weight percent is 3%.
1, crystallinity Mn is prepared0.87Fe0.13PO4Anhydrous compound: the ferric nitrate of 8.7mol manganese chloride, 1.3mol are mixed
In ethanol, 1molH is added while stirring3PO4Solution, at 30 DEG C react 7h after obtain the precipitating of celadon, by product into
Row is filtered, is washed, and obtains amorphous Mn0.87Fe0.13PO4Hydrate, after 80 DEG C of vacuum drying for 24 hours, then in argon gas-hydrogen
Under (95:5) atmosphere, it is roasted into 12h at 750 DEG C, obtains crystallinity Mn0.87Fe0.13PO4Anhydrous compound；
2, hud typed iron manganese phosphate for lithium is prepared: by above-mentioned crystallinity Mn0.87Fe0.13PO4Anhydrous compound and 0.055mol sulphur
Sour manganese, 0.184mol ferrous oxalate, 0.24mol ammonium dihydrogen phosphate and the mixing of 1.24mol lithium hydroxide in deionized water, are stirred
It is transferred in hydrothermal reaction kettle after being formed uniformly suspension, puts it into 175 DEG C of baking oven and react 8h, obtained product carries out
It filters, washing, after being dried for 24 hours at 80 DEG C, then under nitrogen-hydrogen (95:5) atmosphere, roasts 9h at 700 DEG C, crystallized
The hud typed iron manganese phosphate lithium particle of property；
3, it prepares the hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding: above-mentioned hud typed iron manganese phosphate lithium particle is added
Enter into 0.053mol lithium hydroxide aqueous solution, 0.053mol ferrous oxalate and 0.053mol phosphoric acid are instilled while being dispersed with stirring
Ammonium dihydrogen adds 31.4g sucrose, after quickly stirring 20min, is transferred in hydrothermal reaction kettle, is put into 175 DEG C of baking oven
6.5h is reacted, product is filtered, is washed, after being dried for 24 hours at 80 DEG C, then under nitrogen-hydrogen (95:5) atmosphere, in 725
7h is roasted at DEG C, obtains the hud typed iron manganese phosphate lithium particle of lithium iron phosphate/carbon cladding.
The composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity for measuring battery is
150mAh/g, first charge-discharge efficiency 95.9%, capacity retention ratio is 98.1% after recycling 100 weeks.
Method and core concept of the invention that the above embodiments are only used to help understand.It should be pointed out that for
For those skilled in the art, under the premise of the present invention, relevant improve and perfect can also be carried out to the present invention,
These improve and perfects are also fallen within the protection scope of the claims of the present invention.The foregoing description of the disclosed embodiments makes
Professional and technical personnel in the field can be realized or using the present invention.To a variety of improvement of these embodiments to those skilled in the art
It will be apparent for member, the general principles defined herein can be without departing from the scope of the invention, other
It is realized in embodiment.Therefore, the present invention will not be intended to be limited to the embodiments shown herein, but it is public to accord with institute herein
The consistent broader range of the principle and feature opened.
Claims (7)
1. a kind of hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, which is characterized in that it is described it is compound just
It is LiMn that pole material, which forms general formula,xFe1-xPO4/LiMnyFe1-yPO4/LiFePO4/ C, wherein the composition general formula of nuclear material are as follows:
LiMnxFe1-xPO4, the composition general formula of Shell Materials is LiMnyFe1-yPO4, the composition general formula of coating layer material is LiFePO4/ C,
Also, 0.8≤x≤0.9,0.2≤y≤0.4, meanwhile, weight percent shared by nuclear material is 60~80%, shared by Shell Materials
Weight percent is 15~30%, and weight percent shared by LiFePO4 is 3~7% in coating layer material, in coating layer material
Weight percent shared by carbon is 2~3%；
Wherein, the preparation method of the hud typed iron manganese phosphate for lithium composite positive pole of the lithium iron phosphate/carbon cladding includes following
Step:
(1) crystallinity MnxFe1-xPO4Anhydrous compound: it is that x:1-x weighs manganese source, source of iron by the molar ratio of Mn:Fe, is blended in second
In alcohol, H is added in stirring while3PO4Solution obtains the precipitating of celadon after reacting 4~7h at 30 DEG C, product is taken out
Filter, washing under protective atmosphere, in 650~800 DEG C of 10~20h of roasting temperature, obtain after 80 DEG C of vacuum drying for 24 hours
Crystallinity MnxFe1-xPO4Anhydrous compound；
(2) hud typed iron manganese phosphate for lithium: by step (1) crystallinity MnxFe1-xPO4Anhydrous compound and manganese source, source of iron, phosphorus source and
Lithium source stoichiometrically mixes in deionized water, stirs evenly and is transferred in hydrothermal reaction kettle after forming suspension, 150
8~15h is reacted in~200 DEG C of baking oven, product is filtered, is washed, after being dried for 24 hours at 80 DEG C, under protective atmosphere, in
650~800 DEG C of 5~10h of roasting temperature obtain the hud typed iron manganese phosphate lithium particle of crystallinity；
(3) the hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding: the hud typed iron manganese phosphate lithium particle of step (2) is added to
The source of iron and phosphorus source with lithium hydroxide equimolar amounts are instilled in a certain amount of lithium hydroxide aqueous solution, while being dispersed with stirring, then
Be added carbon source, quickly stir 10~60min after, be transferred in hydrothermal reaction kettle, in 150~200 DEG C of baking oven react 5~
Product is filtered, is washed by 8h, after drying for 24 hours at 80 DEG C, under protective atmosphere, in 650~800 DEG C of roasting temperatures 3
~8h obtains the hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding；
The stoichiometric ratio of above-mentioned each substance presses general formula LiMnxFe1-xPO4/LiMnyFe1-yPO4/LiFePO4/ C is determined, wherein
0.8≤x≤0.9,0.2≤y≤0.4, LiMnxFe1-xPO4Shared weight percent is 60~80%, LiMnyFe1-yPO4It is shared
Weight percent is 15~30%, LiFePO4Weight percent shared by LiFePO4 is 3~7%, LiFePO in/C4Carbon institute in/C
Accounting for weight percent is 2~3%.
2. the hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding according to claim 1, feature
It is, the manganese source is one of manganese nitrate, manganese sulfate, manganese chloride, manganese carbonate or two kinds of combinations.
3. the hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding according to claim 1, feature
It is, the source of iron is ferrous oxalate, ferric nitrate, any one or two kinds of combinations in ferrous sulfate.
4. the hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding according to claim 1, feature
It is, phosphorus source is ammonium dihydrogen phosphate.
5. the hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding according to claim 1, feature
It is, the lithium source is one of lithium carbonate, lithium hydroxide or two kinds of combinations.
6. the hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding according to claim 1, feature
It is, the carbon source is one of sucrose, glucose, citric acid, PEG20000 or two kinds of combinations.
7. the hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding according to claim 1, feature
It is, the protective atmosphere is nitrogen, argon gas, 95:5 nitrogen-hydrogen, any one or two kinds in 95:5 argon gas-hydrogen
Combination.
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| CN106981656B (en) * | 2017-05-13 | 2019-12-13 | 合肥国轩高科动力能源有限公司 | Preparation method of battery-grade ferromanganese phosphate |
| TWI625888B (en) * | 2017-07-14 | 2018-06-01 | Hcm Co Ltd | Lithium iron manganese phosphate particles, lithium iron manganese phosphate powder and preparation method thereof |
| CN108557792B (en) * | 2018-01-29 | 2019-10-25 | 蒋央芳 | A kind of preparation method of cladded type iron manganese phosphate |
| CN110803691A (en) * | 2019-11-01 | 2020-02-18 | 浙江天能能源科技股份有限公司 | Lithium manganese iron phosphate cathode material and preparation method thereof |
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| CN111900344B (en) * | 2020-07-02 | 2022-03-29 | 江苏海基新能源股份有限公司 | Preparation method of carbon-coated lithium manganese iron phosphate cathode material |
| CN111908442B (en) * | 2020-08-07 | 2022-12-09 | 上海华谊（集团）公司 | Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof |
| CN114256448A (en) * | 2020-09-25 | 2022-03-29 | 比亚迪股份有限公司 | Lithium iron manganese phosphate composite material, preparation method thereof and lithium ion battery |
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| CN115911291A (en) * | 2021-09-24 | 2023-04-04 | 比亚迪股份有限公司 | Battery positive electrode material and preparation method and application thereof |
| CN114203991A (en) * | 2021-12-01 | 2022-03-18 | 远景动力技术(江苏)有限公司 | Positive electrode material additive, positive electrode and lithium ion battery |
| CN114512649A (en) * | 2022-02-08 | 2022-05-17 | 江苏中兴派能电池有限公司 | Composite lithium manganese iron phosphate cathode material, preparation method and application thereof |
| CN114843507B (en) * | 2022-03-28 | 2023-04-11 | 佛山市德方纳米科技有限公司 | Single-core multi-shell lithium manganese iron phosphate positive electrode material, preparation method and secondary battery |
| WO2023206439A1 (en) * | 2022-04-29 | 2023-11-02 | 宁德时代新能源科技股份有限公司 | Secondary battery, and battery module, battery pack and electric device comprising same |
| CN115724418A (en) * | 2022-12-09 | 2023-03-03 | 广东邦普循环科技有限公司 | Lithium iron manganese phosphate positive electrode material, preparation method thereof and battery |
| CN116581280B (en) * | 2023-07-12 | 2023-09-12 | 深圳海辰储能控制技术有限公司 | Positive electrode material, preparation method thereof, positive electrode plate and lithium battery |
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