CN106340639A - Composite lithium iron phosphate/carbon coated core-shell type lithium ferric manganese phosphate anode material and preparation method thereof - Google Patents
Composite lithium iron phosphate/carbon coated core-shell type lithium ferric manganese phosphate anode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite lithium iron phosphate/carbon coated core-shell type lithium ferric manganese phosphate anode material. The constituent general formula of the composite lithium iron phosphate/carbon coated core-shell type lithium ferric manganese phosphate anode material is LiMnxFe1-xPO4/LiMnyFe1-yPO4/LiFePO4/C, wherein the constituent general formula of a core material is LiMnxFe1-xPO4, the constituent general formula of a shell material is LiMnyFe1-yPO4, the constituent general formula of a coating layer material is LiFePO4/C, and x is greater than or equal to 0.8 but is smaller than or equal to 0.9, and y is greater than or equal to 0.2 but is smaller than or equal to 0.4. In addition, the core material accounts for 60-80% by weight of lithium iron phosphate, and the carbon in the coating layer material accounts for 2-3% by weight of lithium iron phosphate. Core-shell type lithium ferric manganese phosphate particles are obtained by adopting a coprecipitation method and a hydrothermal method and then are mixed with a lithium source, an iron source, a phosphorus source and a carbon source to perform hydrothermal reaction so as to obtain a target product. The product particles prepared by adopting the method are regular in spherical morphology, the dissolution of manganese in the anode material is greatly reduced, and the cycle performance of a battery is remarkably improved.
Description
Technical field
The invention belongs to technical field of new energy material preparation, specifically a kind of hud typed phosphorus of lithium iron phosphate/carbon cladding
Sour ferromanganese lithium composite positive pole and preparation method thereof.
Background technology
With the increasingly depleted of petroleum resources, energy problem has become as human social strategy and has to solve
Important topic certainly.In recent years, lithium ion battery because having that running voltage is high, energy density is big, have extended cycle life, memoryless effect
Should, small volume, lightweight, non-environmental-pollution the advantages of, obtain and develop faster, wherein positive electrode is lithium ion battery
One of four important component parts, the chemical property to lithium ion battery and security performance have prayed vital effect,
And its cost is also close to the nearly half of whole lithium ion battery totle drilling cost.The research and development of therefore positive electrode are always people's research
Emphasis.
Phosphate of olivine type base anode material limpo4(m=fe, mn, co and ni etc.) has with respect to layered cathode material
Stability Analysis of Structures, cost benefit and environmental friendliness is had to be paid close attention in a large number.Wherein olivine-type lifepo4Due to stablizing of structure
Property is widely used as the positive electrode of lithium ion battery, but relatively low (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 having higher voltage (4.0v vs.
li+/ li), and theoretical energy density compares lifepo4Big 20%, and theoretical specific capacity and lifepo4Close (~ 170mah g-1), inhale
Draw substantial amounts of concern.However, its electronic conductivity compares lifepo4Lower it is considered to be insulator so as to discharge capacity low,
High rate performance is poor, and mn can occur dissolving to make capability retention poor and mn in cyclic process3+The jahn- occurring
Teller distorts, and limits limnpo4Application.
Find that mn and fe can form limn through substantial amounts of research1-xfexpo4Solid solution, has similar lifepo4Olive
Olive stone structure.Its running voltage is in 3.5 ~ 4.1v it is adaptable to the stable electrochemical window of traditional electrolyte liquid system.Can protect
Improve high rate performance and the cycle performance of material while card specific capacity.General higher fe content can reduce the dissolution of mn,
Thus improving the cycle performance of material, make limn1-xfexpo4Become the most promising positive electrode of high performance lithium ion battery it
One.
In order to improve limn1-xfexpo4The performance of positive electrode is it is necessary to the major issue solving is exactly the molten of mn
Solution.Solve limn at present1-xfexpo4The method of positive electrode dissolving has positive electrode Surface coating, ion doping, changes electrolysis
Liquid etc..
In view of the present situation of prior art, the present inventor has carried out deeply widely grinding 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, reduce the dissolving of mn, significantly improve the cycle performance of material.
Content of the invention
It is an object of the invention to the defect overcoming prior art to exist, provide that a kind of safety is good, heat stability is high, energy
Substantially reduce mn dissolving, improve material cycle performance the features such as lithium iron phosphate/carbon cladding hud typed iron manganese phosphate for lithium multiple
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, described composite positive pole composition is logical
Formula is limnxfe1-xpo4/limnyfe1-ypo4/lifepo4/ c, wherein, the composition formula of nuclear material is: limnxfe1-xpo4, shell
The composition formula of layer material is limnyfe1-ypo4, the composition formula of coating layer material is lifepo4/ c, and, 0.8≤x≤
0.9,0.2≤y≤0.4, meanwhile, percetage by weight shared by nuclear material be 60 ~ 80%, percetage by weight shared by Shell Materials be 15 ~
30%, percetage by weight shared by LiFePO4 in coating layer material be 3 ~ 7%, percetage by weight shared by carbon in coating layer material be 2 ~
3%.
Further object is that providing a kind of hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding to be just combined
The preparation method of pole material, the method comprising the steps of:
(1) crystallinity mnxfe1-xpo4Anhydrous compound: weigh manganese source, source of iron by the mol ratio of mn:fe for x:1-x, be blended in
In ethanol, while stirring, add h3po4Solution, obtains the precipitation of celadon, product is taken out after reaction 4 ~ 7h at 30 DEG C
Filter, washing, after 80 DEG C of vacuum drying 24h, under protective atmosphere, in 650 ~ 800 DEG C of roasting temperature 10 ~ 20h, are tied
Crystalline substance 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, is transferred in hydrothermal reaction kettle, 150 after the formation suspension that stirs
8 ~ 15h is reacted, product carries out sucking filtration, washing in ~ 200 DEG C of baking oven, after drying 24h at 80 DEG C, under protective atmosphere, in
650 ~ 800 DEG C of roasting temperature 5 ~ 10h, obtain crystallinity hud typed iron manganese phosphate lithium particle；
(3) the hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding: hud typed for step (2) iron manganese phosphate lithium particle is added to
In a certain amount of lithium hydroxide aqueous solution, while dispersed with stirring, instill source of iron and the phosphorus source with Lithium hydrate equimolar amountss, then
Add carbon source, quickly after stirring 10 ~ 60min, transfer in hydrothermal reaction kettle, in 150 ~ 200 DEG C of baking oven, react 5 ~ 8h, will
Product carries out sucking filtration, washing, after drying 24h at 80 DEG C, under protective atmosphere, in 650 ~ 800 DEG C of roasting temperature 3 ~ 8h, obtains
Hud typed iron manganese phosphate for lithium composite positive pole to lithium iron phosphate/carbon cladding；
The stoichiometric proportion of above-mentioned each material presses formula limnxfe1-xpo4/limnyfe1-ypo4/lifepo4/ c determining, its
In, 0.8≤x≤0.9,0.2≤y≤0.4, limnxfe1-xpo4Shared percetage by weight is 60 ~ 80%, limnyfe1-ypo4Shared
Percetage by weight is 15 ~ 30%, lifepo4Percetage by weight shared by LiFePO4 in/c is 3 ~ 7%, lifepo4Weight shared by carbon in/c
Amount percent is 2 ~ 3%.
Preferably, described manganese source is one of manganese nitrate, manganese sulfate, manganese chloride, manganese carbonate or two kinds of combinations.
Preferably, described source of iron be Ferrox., ferric nitrate, any one or two kinds of combinations in ferrous sulfate.
Preferably, phosphorus source is ammonium dihydrogen phosphate.
Preferably, described lithium source is one of lithium carbonate, Lithium hydrate or two kinds of combinations.
Preferably, described carbon source is one of sucrose, glucose, citric acid, peg20000 or two kinds of combinations.
Preferably, described protective atmosphere be nitrogen, argon, nitrogen-hydrogen (95:5), in argon-hydrogen (95:5)
Any one or two kinds combination.
Beneficial effects of the present invention: the present invention is prepared for iron phosphate using the method that coprecipitation and hydro-thermal method combine
The hud typed iron manganese phosphate for lithium composite positive pole of lithium/carbon coating.In nucleocapsid structure, in nuclear material, the content of mn is high, provides material
Expect higher voltage and high power capacity, and in Shell Materials, the content of mn is less, decreases the dissolving of mn in material, clad is by phosphorus
Sour ferrum lithium/carbon composition, prevents the contact that core-shell material is with electrolyte further, reduces the dissolving of mn, carbon prevents simultaneously
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 combined
Positive electrode has higher specific capacity, and cycle performance is excellent；Preparation method of the present invention is simple, safe, easily operated.
Brief description
The structural representation of the iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding that Fig. 1 embodiment 1 prepares
Figure, wherein 1 is the core of rich mn, and 2 is the shell of rich fe, and 3 is lifepo4/ c clad；
The sem figure of the iron manganese phosphate for lithium composite positive pole section of the lithium iron phosphate/carbon cladding that Fig. 2 prepares for embodiment 1
Piece；
The iron manganese phosphate for lithium composite positive pole assembling of the lithium iron phosphate/carbon cladding that Fig. 3 prepares for the embodiment of the present invention 1
The cyclic curve of battery；
Fig. 4 is the cyclic curve of the battery of non-hud typed lithium iron manganese phosphate anode material assembling of comparative example carbon coating.
Specific embodiment
With specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.
A kind of composition formula of hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon of present invention cladding is
limnxfe1-xpo4/limnyfe1-ypo4/lifepo4/ c, wherein, the composition formula of nuclear material is: limnxfe1-xpo4, shell material
The composition formula of material is limnyfe1-ypo4, the composition formula of coating layer material is lifepo4/ c, and, 0.8≤x≤0.9,
0.2≤y≤0.4, meanwhile, percetage by weight shared by nuclear material is 60 ~ 80%, and percetage by weight shared by Shell Materials is 15 ~ 30%,
Percetage by weight shared by LiFePO4 in coating layer material is 3 ~ 7%, and percetage by weight shared by carbon in coating layer material is 2 ~ 3%,
In the embodiment of the present invention, the stoichiometric proportion of each material is according to the x in formula, and the part by weight of y and each component is being calculated
's.
Embodiment 1
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, its composition formula is: limn0.9fe0.1po4/
limn0.2fe0.8po4/lifepo4Percetage by weight shared by/c, wherein nuclear material is 80%, and percetage by weight shared by Shell Materials is
15%, percetage by weight shared by LiFePO4 in coating layer material is 3%, and percetage by weight shared by carbon in coating layer material is 2%.
1st, prepare crystallinity mn0.9fe0.1po4Anhydrous compound: the Ferrox. of 9mol manganese nitrate, 1mol is blended in second
In alcohol, while stirring, add 1molh3po4Solution, obtains the precipitation of celadon, product is taken out after reaction 4h at 30 DEG C
Filter, washing, obtain amorphous mn0.9fe0.1po4Hydrate, after 80 DEG C of vacuum drying 24h, more in a nitrogen atmosphere, by its
At 800 DEG C, roasting 10h, obtains crystallinity mn0.9fe0.1po4Anhydrous compound；
2nd, prepare hud typed iron manganese phosphate for lithium: by above-mentioned crystallinity mn0.9fe0.1po4Anhydrous compound and 0.037mol manganese nitrate,
0.149mol Ferrox., 0.19mol ammonium dihydrogen phosphate and 0.59mol lithium carbonate mix in deionized water, and stir shape
Be transferred in hydrothermal reaction kettle after becoming suspension, put it in 150 DEG C of baking oven reaction 15h, the product obtaining carry out sucking filtration,
Washing, after drying 24h at 80 DEG C, more in a nitrogen atmosphere, roasting 5h at 800 DEG C, obtain the hud typed iron manganese phosphate of crystallinity
Lithium particle；
3rd, prepare 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 to
In 0.037mol lithium hydroxide aqueous solution, while dispersed with stirring, instill 0.037mol Ferrox. and 0.037mol biphosphate
Ammonium, adds 19.6g sucrose, after quick stirring 60min, transfers in hydrothermal reaction kettle, it puts into reaction in 150 DEG C of baking oven
8h, product is carried out sucking filtration, washing, and after drying 24h at 80 DEG C, more in a nitrogen atmosphere, at 650 DEG C, roasting 8h, obtains phosphorus
The hud typed iron manganese phosphate lithium particle of sour ferrum lithium/carbon coating.
This composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity recording battery is
150mah/g, first charge-discharge efficiency is 94.5%, and after circulating 100 weeks, capability retention is 98.2%.
The structural representation of the iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding that Fig. 1 embodiment 1 prepares
Figure, wherein 1 is the core of rich mn, and 2 is the shell of rich fe, and 3 is lifepo4/ c clad；Fig. 2 prepares for embodiment 1
The sem picture of the iron manganese phosphate for lithium composite positive pole section of lithium iron phosphate/carbon cladding；Fig. 3 is prepared into for the embodiment of the present invention 1
The cyclic curve of the battery of iron manganese phosphate for lithium composite positive pole assembling of the lithium iron phosphate/carbon cladding arriving.
Comparative example
The non-hud typed lithium iron manganese phosphate anode material of carbon coating, its composition formula is: limn0.9fe0.1po4/ c, wherein phosphoric acid
Ferromanganese lithium accounts for 95%, and carbon coating layer accounts for 5%.
9mol manganese nitrate, 1mol Ferrox., 10mol ammonium dihydrogen phosphate and 5mol lithium carbonate mix in deionized water,
Add 413g sucrose, be transferred in hydrothermal reaction kettle after the formation suspension that stirs, put it into anti-in 150 DEG C of baking oven
Answer 15h, the product obtaining carries out sucking filtration, washing, after drying 24h at 80 DEG C, more in a nitrogen atmosphere, roasting 5h at 800 DEG C,
Obtain the non-hud typed lithium iron manganese phosphate anode material of carbon coating.
Fig. 4 is the cyclic curve of the battery of non-hud typed lithium iron manganese phosphate anode material assembling of comparative example carbon coating.
Embodiment 2
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, its composition formula is:
limn0.85fe0.15po4/limn0.3fe0.7po4/lifepo4Percetage by weight shared by/c, wherein nuclear material is 70%, Shell Materials
Shared percetage by weight is 20%, and percetage by weight shared by LiFePO4 in coating layer material is 7%, shared by carbon in coating layer material
Percetage by weight is 3%.
1st, prepare crystallinity mn0.85fe0.15po4Anhydrous compound: by the ferric nitrate mixing of 8.5mol manganese sulfate, 1.5mol
In ethanol, add 1molh while stirring3po4Solution, obtains the precipitation of celadon, product is entered after reaction 7h at 30 DEG C
Row sucking filtration, washing, obtain amorphous mn0.85fe0.15po4Hydrate, after 80 DEG C of vacuum drying 24h, more under an argon atmosphere,
By it at 700 DEG C roasting 20h, obtain crystallinity mn0.85fe0.15po4Anhydrous compound；
2nd, prepare hud typed iron manganese phosphate for lithium: by above-mentioned crystallinity mn0.85fe0.15po4Anhydrous compound and 0.085mol sulphuric acid
Manganese, 0.199mol ferric nitrate, 0.28mol ammonium dihydrogen phosphate and 1.28mol Lithium hydrate mix in deionized water, stir
It is transferred in hydrothermal reaction kettle after forming suspension, puts it into reaction 8h in 200 DEG C of baking oven, the product obtaining is taken out
Filter, washing, after drying 24h at 80 DEG C, more under an argon atmosphere, roasting 10h at 700 DEG C, obtain the hud typed phosphoric acid of crystallinity
Ferromanganese lithium particle；
3rd, prepare 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 to
In 0.10mol lithium hydroxide aqueous solution, while dispersed with stirring, instill 0.10mol ferric nitrate and 0.10mol ammonium dihydrogen phosphate, then
Add 33.6g glucose, after quick stirring 10min, transfer in hydrothermal reaction kettle, it puts into reaction 5h in 200 DEG C of baking oven,
Product is carried out sucking filtration, washing, after drying 24h at 80 DEG C, more under an argon atmosphere, roasting 3h, obtains iron phosphate at 800 DEG C
The hud typed iron manganese phosphate lithium particle of lithium/carbon coating.
This composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity recording battery is
152 mah/g, first charge-discharge efficiency is 95.5%, and after circulating 100 weeks, capability retention is 97.8%.
Embodiment 3
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, its composition formula is: limn0.8fe0.2po4/
limn0.4fe0.6po4/lifepo4Percetage by weight shared by/c, wherein nuclear material is 60%, and percetage by weight shared by Shell Materials is
30%, percetage by weight shared by LiFePO4 in coating layer material is 7%, and percetage by weight shared by carbon in coating layer material is 3%.
1st, prepare crystallinity mn0.8fe0.2po4Anhydrous compound: the ferric nitrate of 8.0mol manganese sulfate, 2.0mol is blended in
In ethanol, while stirring, add 1molh3po4Solution, obtains the precipitation of celadon, product is carried out after reaction 6h at 30 DEG C
Sucking filtration, washing, obtain amorphous mn0.8fe0.2po4Hydrate, after 80 DEG C of vacuum drying 24h, then at argon-hydrogen (95:5)
Under atmosphere, by it at 650 DEG C roasting 15h, obtain crystallinity mn0.8fe0.2po4Anhydrous compound；
2nd, prepare hud typed iron manganese phosphate for lithium: by above-mentioned crystallinity mn0.8fe0.2po4Anhydrous compound and 0.20mol manganese chloride,
0.299mol ferrous sulfate, 0.5mol ammonium dihydrogen phosphate and 1.5mol Lithium hydrate mix in deionized water, and stir shape
Be transferred in hydrothermal reaction kettle after becoming suspension, put it in 170 DEG C of baking oven reaction 10h, the product obtaining carry out sucking filtration,
Washing, after drying 24h at 80 DEG C, then under argon-hydrogen (95:5) atmosphere, roasting 7h at 650 DEG C, obtain crystallinity nucleocapsid
Type iron manganese phosphate lithium particle；
3rd, prepare 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 to
In 0.116mol lithium hydroxide aqueous solution, while dispersed with stirring, instill 0.116mol ferrous sulfate and 0.116mol biphosphate
Ammonium, adds 39.3g citric acid, after quick stirring 30min, transfers in hydrothermal reaction kettle, it puts into anti-in 180 DEG C of baking oven
Answer 7h, product is carried out sucking filtration, washing, after drying 24h at 80 DEG C, then under argon-hydrogen (95:5) atmosphere, at 700 DEG C
Roasting 5h, obtains the hud typed iron manganese phosphate lithium particle of lithium iron phosphate/carbon cladding.
This composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity recording battery is
149 mah/g, first charge-discharge efficiency is 95.9%, and after circulating 100 weeks, capability retention is 97.1%.
Embodiment 4
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, its composition formula is: limn0.8fe0.2po4/
limn0.25fe0.75po4/lifepo4Percetage by weight shared by/c, wherein nuclear material is 75%, percetage by weight shared by Shell Materials
For 17.5%, percetage by weight shared by LiFePO4 in coating layer material is 5%, and percetage by weight shared by carbon in coating layer material is
2.5%.
1st, prepare crystallinity mn0.8fe0.2po4Anhydrous compound: the ferric nitrate of 8.0mol manganese carbonate, 2.0mol is blended in
In ethanol, while stirring, add 1molh3po4Solution, obtains the precipitation of celadon, product is carried out after reaction 5h at 30 DEG C
Sucking filtration, washing, obtain amorphous mn0.8fe0.2po4Hydrate, after 80 DEG C of vacuum drying 24h, then at nitrogen-hydrogen (95:5)
Under atmosphere, by it at 650 DEG C roasting 20h, obtain crystallinity mn0.8fe0.2po4Anhydrous compound；
2nd, prepare hud typed iron manganese phosphate for lithium: by above-mentioned crystallinity mn0.8fe0.2po4Anhydrous compound and 0.058mol manganese carbonate,
0.174mol ferric nitrate, 0.23mol ammonium dihydrogen phosphate and 0.62mol lithium carbonate mix in deionized water, stir and are formed
It is transferred to after suspension in hydrothermal reaction kettle, puts it into reaction 9h in 170 DEG C of baking oven, the product obtaining carries out sucking filtration, washes
Wash, after drying 24h at 80 DEG C, then under nitrogen-hydrogen (95:5) atmosphere, at 650 DEG C, roasting 5h, obtains crystallinity hud typed
Iron manganese phosphate lithium particle；
3rd, prepare 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 to
In 0.066mol lithium hydroxide aqueous solution, while dispersed with stirring, instill 0.066mol ferric nitrate and 0.066mol biphosphate
Ammonium, adds 26.2gpeg20000, after quick stirring 50min, transfers in hydrothermal reaction kettle, it is put in 170 DEG C of baking oven
Reaction 6h, product is carried out sucking filtration, washing, after drying 24h at 80 DEG C, then under nitrogen-hydrogen (95:5) atmosphere, in 750 DEG C
Lower roasting 4h, obtains the hud typed iron manganese phosphate lithium particle of lithium iron phosphate/carbon cladding.
This composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity recording battery is
147mah/g, first charge-discharge efficiency is 94.9%, and after circulating 100 weeks, capability retention is 97.5%.
Embodiment 5
The hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding, its composition formula is:
limn0.87fe0.13po4/limn0.23fe0.77po4/lifepo4Percetage by weight shared by/c, wherein nuclear material is 75%, shell material
Percetage by weight shared by material is 18%, and percetage by weight shared by LiFePO4 in coating layer material is 4%, carbon institute in coating layer material
Accounting for percetage by weight is 3%.
1st, prepare crystallinity mn0.87fe0.13po4Anhydrous compound: by the ferric nitrate mixing of 8.7mol manganese chloride, 1.3mol
In ethanol, add 1molh while stirring3po4Solution, obtains the precipitation of celadon, product is entered after reaction 7h at 30 DEG C
Row sucking filtration, washing, obtain amorphous mn0.87fe0.13po4Hydrate, after 80 DEG C of vacuum drying 24h, then in argon-hydrogen
(95:5) under atmosphere, by it at 750 DEG C roasting 12h, obtain crystallinity mn0.87fe0.13po4Anhydrous compound；
2nd, prepare hud typed iron manganese phosphate for lithium: by above-mentioned crystallinity mn0.87fe0.13po4Anhydrous compound and 0.055mol sulphuric acid
Manganese, 0.184mol Ferrox., 0.24mol ammonium dihydrogen phosphate and 1.24mol Lithium hydrate mix in deionized water, and stirring is all
It is transferred in hydrothermal reaction kettle after even formation suspension, puts it into reaction 8h in 175 DEG C of baking oven, the product obtaining is taken out
Filter, washing, after drying 24h at 80 DEG C, then under nitrogen-hydrogen (95:5) atmosphere, at 700 DEG C, roasting 9h, obtains crystallinity
Hud typed iron manganese phosphate lithium particle；
3rd, prepare 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 to
In 0.053mol lithium hydroxide aqueous solution, while dispersed with stirring, instill 0.053mol Ferrox. and 0.053mol biphosphate
Ammonium, adds 31.4g sucrose, after quick stirring 20min, transfers in hydrothermal reaction kettle, it puts into reaction in 175 DEG C of baking oven
6.5h, product is carried out sucking filtration, washing, after drying 24h at 80 DEG C, then under nitrogen-hydrogen (95:5) atmosphere, at 725 DEG C
Roasting 7h, obtains the hud typed iron manganese phosphate lithium particle of lithium iron phosphate/carbon cladding.
This composite positive pole and lithium are assembled into button cell to electrode, the first discharge specific capacity recording battery is
150mah/g, first charge-discharge efficiency is 95.9%, and after circulating 100 weeks, capability retention is 98.1%.
The explanation of above example is only intended to help and understands the method for the present invention and core concept.It should be pointed out that for
For those skilled in the art, on the premise of the present invention, the present invention can also be carried out with the improvement and perfect of correlation,
These improve and improve and also fall in the protection domain of the claims in the present invention.Described above to the disclosed embodiments, makes
Professional and technical personnel in the field are capable of or use the present invention.To multiple improvement of these embodiments to those skilled in the art
Will be apparent from for member, generic principles defined herein can be without departing from the scope of the invention, in other
Realize in embodiment.Therefore, the present invention will not be intended to be limited to the embodiments shown herein, and is intended to accord with institute's public affairs herein
The principle opened and the consistent broader scope of feature.
Claims (8)
1. a kind of hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding is it is characterised in that described be just combined
Pole material composition formula is limnxfe1-xpo4/limnyfe1-ypo4/lifepo4/ c, wherein, the composition formula of nuclear material is:
limnxfe1-xpo4, the composition formula of Shell Materials is limnyfe1-ypo4, the composition formula of coating layer material is lifepo4/ c,
And, 0.8≤x≤0.9,0.2≤y≤0.4, meanwhile, percetage by weight shared by nuclear material is 60 ~ 80%, weight shared by Shell Materials
Amount percent is 15 ~ 30%, and percetage by weight shared by LiFePO4 in coating layer material is 3 ~ 7%, shared by carbon in coating layer material
Percetage by weight is 2 ~ 3%.
2. a kind of system of the hud typed iron manganese phosphate for lithium composite positive pole of lithium iron phosphate/carbon cladding as claimed in claim 1
Preparation Method is it is characterised in that the method comprising the steps of:
(1) crystallinity mnxfe1-xpo4Anhydrous compound: weigh manganese source, source of iron by the mol ratio of mn:fe for x:1-x, be blended in second
In alcohol, while stirring, add h3po4Solution, obtains the precipitation of celadon, product is taken out after reaction 4 ~ 7h at 30 DEG C
Filter, washing, after 80 DEG C of vacuum drying 24h, under protective atmosphere, in 650 ~ 800 DEG C of roasting temperature 10 ~ 20h, are tied
Crystalline substance 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, is transferred in hydrothermal reaction kettle, 150 after the formation suspension that stirs
8 ~ 15h is reacted, product carries out sucking filtration, washing in ~ 200 DEG C of baking oven, after drying 24h at 80 DEG C, under protective atmosphere, in
650 ~ 800 DEG C of roasting temperature 5 ~ 10h, obtain crystallinity hud typed iron manganese phosphate lithium particle；
(3) the hud typed iron manganese phosphate for lithium of lithium iron phosphate/carbon cladding: hud typed for step (2) iron manganese phosphate lithium particle is added to
In a certain amount of lithium hydroxide aqueous solution, while dispersed with stirring, instill source of iron and the phosphorus source with Lithium hydrate equimolar amountss, then
Add carbon source, quickly after stirring 10 ~ 60min, transfer in hydrothermal reaction kettle, in 150 ~ 200 DEG C of baking oven, react 5 ~ 8h, will
Product carries out sucking filtration, washing, after drying 24h at 80 DEG C, under protective atmosphere, in 650 ~ 800 DEG C of roasting temperature 3 ~ 8h, obtains
Hud typed iron manganese phosphate for lithium composite positive pole to lithium iron phosphate/carbon cladding；
The stoichiometric proportion of above-mentioned each material presses formula limnxfe1-xpo4/limnyfe1-ypo4/lifepo4/ c determining, wherein,
0.8≤x≤0.9,0.2≤y≤0.4, limnxfe1-xpo4Shared percetage by weight is 60 ~ 80%, limnyfe1-ypo4Shared weight
Amount percent is 15 ~ 30%, lifepo4Percetage by weight shared by LiFePO4 in/c is 3 ~ 7%, lifepo4Weight shared by carbon in/c
Percent is 2 ~ 3%.
3. preparation method according to claim 2 it is characterised in that described manganese source be manganese nitrate, manganese sulfate, manganese chloride,
One of manganese carbonate or two kinds of combinations.
4. preparation method according to claim 2 it is characterised in that described source of iron be Ferrox., ferric nitrate, sulphuric acid sub-
Any one in ferrum or two kinds of combinations.
5. preparation method according to claim 2 is it is characterised in that phosphorus source is ammonium dihydrogen phosphate.
6. preparation method according to claim 2 it is characterised in that described lithium source be lithium carbonate, in Lithium hydrate one
Plant or two kinds of combinations.
7. preparation method according to claim 2 it is characterised in that described carbon source be sucrose, glucose, citric acid,
One of peg20000 or two kinds of combinations.
8. preparation method according to claim 2 it is characterised in that described protective atmosphere be nitrogen, argon, nitrogen-
Any one in hydrogen (95:5), argon-hydrogen (95:5) or two kinds of combinations.
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