CN103456954A - Preparation method of active electrode material - Google Patents
Preparation method of active electrode material Download PDFInfo
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- CN103456954A CN103456954A CN2013104033936A CN201310403393A CN103456954A CN 103456954 A CN103456954 A CN 103456954A CN 2013104033936 A CN2013104033936 A CN 2013104033936A CN 201310403393 A CN201310403393 A CN 201310403393A CN 103456954 A CN103456954 A CN 103456954A
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Abstract
The invention discloses a preparation method of an active electrode material by using low-price raw materials, and belongs to the field of active electrode materials. In the active electrode material, M is a first element, A is a second element, X is a metalloid element, and Z is a precursor. The preparation method comprises the following steps: a, forming an intermediate compound by using an M-source compound of the first element, an X-source compound of the metalloid element and the precursor Z; b, measuring the contents of the first element M and the metalloid element X in the intermediate compound, adding an A-source compound of the second element and a carbon-source compound according to a certain mole ratio to prepare the intermediate compound, ball-milling and drying; c, calcining the intermediate mixture in oxygen-free atmosphere so as to obtain the active electrode material. According to the preparation method provided by the invention, the low-price materials are completely converted into the precursor firstly, the content of each effective element is measured, re-blending is performed, and then the next preparation for the electrode material is performed; low-price compounds or byproducts can be utilized as raw materials, thus the production cost is reduced.
Description
Technical field
The invention belongs to the active electrode material field, particularly the cheap raw material of a kind of use prepare the method for active electrode material.
Background technology
Lead-acid battery is the most traditional rechargeable battery, has and reaches 150 years applicating histories, because it manufactures simple cheap use always.The lead-acid battery energy density is low, and cycle life is short, the defects such as murder by poisoning of environment has been not suitable for to the needs of New Times.
Lithium ion battery after development of new techniques has that energy density is high to have extended cycle life, and the thermally-stabilised characteristics such as good, can be used as electrokinetic cell.But high because of electrode material and the battery preparation cost of lithium ion battery, be difficult at present in marketing, replace cheap lead-acid battery.
Recently the deionized water solution battery AIB (aqueous ion battery) of development because of its electrode material and manufacturing cost all very low, cycle performance, than lead-acid battery excellence, gets a good chance of replacing in the near future the lead-acid battery that environment is poisoned.Though deionized water solution battery AIB environmental protection, energy density the same as lead-acid battery is low and can only, for energy-storage battery, can't be applied in high power high power capacity electrokinetic cell field.
How preparing at a low price lithium ion battery electrode material, reduce the lithium ion battery manufacturing cost, is one of the key factor that can promote on market of lithium ion battery.
The present invention is that relation prepares cheap electrode material, and from the cheapest raw material of price, process and method through unique, prepare cheap electrode material.
Industry prepares the iron phosphate lithium electrode material, traditional production technology is that ferrous oxalate is as the source of iron raw material, ammonium dihydrogen phosphate is as phosphorus source raw material, two manufacture of materials produce cost, production process is emitted environmentally harmful gas, the production technology that more and more accounts at present main flow is to make source of iron and phosphorus source raw material with ferric phosphate, and ferric phosphate production also produces cost.
Prepare the iron phosphate lithium electrode material, cheap P source compound is phosphoric acid or phosphorus pentoxide, and cheap ferrous source material is iron powder, or other industrial byproduct is such as ferrous sulfate (titanium dioxide industry production byproduct), such as ferrophosphorus (Fe
xp, yellow phosphorus industry is produced byproduct), such as the byproduct ferric phosphate (Fe from ferrophosphorus smelting extraction noble metal vanadium cobalt nickel
xpO
4).
Prepare the phosphate compound electrode material, cheap P source compound is phosphoric acid or phosphorus pentoxide, and cheap Ti source compound is TiOSO
4and Ti (SO
4)
2,, cheap V source compound is NH
4vO
3.
Above-mentioned cheap material fails directly to be used for preparing electrode material sometimes, and one of reason does not have effective method to guarantee that raw material transform fully, and the unconverted Magnetic Materials of minute quantity may be very large to the performance impact of electrode material.Former therefore two, certain variation occurs in the proportioning of each element in conversion process, if do next step preparation by proportioning before transforming, certainly will cause mixing ratio error, affects the performance of electrode material.
The inventive method, after above-mentioned cheap material is transformed fully, redeterminate each effectively without plain content, and each is effectively prepared burden again without plain content by new mensuration, then carries out next step preparation of electrode material.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can overcome active electrode material and prepare the too high shortcoming of expense, can utilize cheap compound and other industrial byproduct to prepare the method for active electrode material as raw material.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of active electrode material, the molecular formula of active electrode material is A
am
b(XO
4)
cz
d,, wherein M is the first element, and A is the second element, and X is metalloid element, and Z is presoma, the preparation method comprises the steps:
A, with the first element M source compound, metalloid element X source compound and presoma are Z-shaped, become intermediate;
B, measure the first element M and the content of metalloid element X in intermediate, according to A ︰ M ︰ X=1.03～1.1 ︰ 1 ︰ 1 mol ratios, add the second elements A source compound and carbon-source cpd, be made into intermediate blend;
C, ball milling and dry described intermediate blend;
D, in oxygen-free atmosphere the calcining described intermediate blend, obtain active electrode material;
Wherein, described the first element M is at least one in transition metal unit Fe, Mn, V, Co, Ni, Al, Mg, Si, Ca, Sr, Ti, Cd, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ta, W, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;
Described the second elements A is at least one in alkali metal Li, Na or K;
Described metalloid element X is at least one in P, Si, S, Al, Ga, N or V;
Described presoma Z is at least one in OH, F, Cl or Br;
Described a, b and c are greater than zero number, and d is more than or equal to zero number.
Wherein, described a, b and c are that 1, d is zero, and described metalloid element X is P, and the molecular formula of active electrode material is AMPO
4, the preparation method comprises the steps:
A, with P source compound and the first element M source compound, make the phosphate compound;
B, the content of measuring the first element M in the phosphate compound and the content of phosphorus, according to A ︰ M ︰ P=1.03～1.1 ︰ 1 ︰ 1 mol ratios add the second elements A source compound, and carbon-source cpd is made intermediate blend; The weight of carbon-source cpd is 1～30% of intermediate blend weight;
C, ball milling and dry described intermediate blend;
D, in oxygen-free atmosphere the calcining described intermediate blend, obtain active phosphate electrode material AMPO
4.
Wherein, in said method, the phosphate compound is to be prepared by following steps: add reaction in phosphate aqueous solution to make the first mixture the first element M source compound, stir; Splash into aqueous hydrogen peroxide solution and stir in the first mixture after stirring, obtaining the second mixture; Make the phosphate compound with the second mixture.
Wherein, in said method, the second mixture is made phosphate compound method and is: the phosphate compound that centrifugation the second mixture must be wet or centrifugation are also washed phosphate compound that the second mixture gained is wet or phosphate compound that centrifugation, washing dry the second mixture must be done.
Wherein, in said method, the first mixture mixing time is between 0.5～5 hour, and the second mixture mixing time is between 3～15 hours; In phosphate aqueous solution, the weight content of phosphoric acid is 10～50%, and in aqueous hydrogen peroxide solution, the hydrogen peroxide weight content is 5～27%, and the pH value of the first mixture of gained is less than 2.5.
Wherein, in said method, described calcining heat is between 250～900 ℃, and calcination time is between 6～15 hours.
Wherein, in said method, described P source compound is at least one in phosphoric acid, phosphorus pentoxide.
Wherein, in said method, the first element M is Fe, and the molecular formula of active electrode material is AFePO
4, the second elements A source compound is Li
2cO
3, LiOH, Li
2o, Na
2cO
3, NaOH, Na
2o, K
2cO
3, KOH or K
2at least one in O.
Wherein, in said method, the first elemental iron source compound and P source compound are all ferrophosphorus (Fe
xp).
Ferrophosphorus is the byproduct of phosphorus production.
Further, intermediate compound is to be prepared by following steps: with the first elemental iron source compound and P source compound ferrophosphorus and the second elements A source compound, according to mol ratio A ︰ Fe=1.05～1.10 ︰ 1, be mixed to get the first mixture; The first mixture is calcined 2～12 hours under aerobic conditions between 250～600 ℃, and after cool to room temperature, this mixture of ball milling, obtain the second mix powder; Measure the content of iron in the second mix powder, phosphorus and the second elements A, according to A ︰ Fe ︰ P=1.03～1.1 ︰ 1 ︰ 1 mol ratios, prepared burden and add carbon-source cpd, blend together intermediate blend; The weight of carbon-source cpd is 1～30% of intermediate blend weight.
Wherein, in said method, the first element M is Fe, and the second elements A is Li, and the molecular formula of active electrode material is LiFePO
4, described the first element M source compound is at least one in iron powder, ferric oxide powder, ferroferric oxide powder, ferrous sulfate powder or ferric phosphate powder.
Wherein, described active electrode material LiFePO
4in, Li ︰ Fe ︰ P mol ratio approaches 1 ︰ 1 ︰ 1 as far as possible.
Ferrous sulfate is the byproduct of titanium white production.Ferric phosphate (Fe
xpO
4) be ferrophosphorus (Fe
xp) refine the byproduct after the noble metal such as vanadium cobalt nickel.
Wherein, in said method, the first element M is Fe and Mn, and the second elements A is Li, and the molecular formula of active electrode material is LiFe
xmn
(1-X)pO
4, the first element M source compound is at least one in iron powder, ferric oxide powder, ferroferric oxide powder, ferrous sulfate powder or ferric phosphate powder, and at least one in manganese powder, manganese dioxide powder.
Wherein, described active electrode material LiFe
xmn
(1-X)pO
4in, (Fe+Mn) ︰ P mol ratio approaches 1 ︰ 1 ︰ 1 to Li ︰ as far as possible.
The present invention also provides the preparation method of another kind of active electrode material, and the molecular formula of active electrode material is ATi
2(PO
4)
3, the preparation method comprises the steps:
A, make the compound of Ti oxide and water with the Ti source compound;
In the compound of b, measurement Ti oxide and water, the content of Ti, add A source compound and P source compound according to A ︰ Ti ︰ P=1 ︰ 2 ︰ 3 mol ratios, and carbon-source cpd is made intermediate blend; The weight of carbon-source cpd is 0～30% of intermediate blend weight;
C, ball milling and dry described intermediate blend;
D, in oxygen-free atmosphere the calcining described intermediate blend, obtain active phosphate electrode material ATi
2(PO
4)
3.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, the A source compound is Li
2cO
3, LiOH, Li
2o, Na
2cO
3, NaOH, Na
2o, K
2cO
3, KOH or K
2at least one in O.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, A is Na, and the molecular formula of active electrode material is NaTi
2(PO
4)
3, the Ti source compound is TiO
2, Ti
2(PSO
4)
3, TiOSO
4in at least one.
Wherein, it will be appreciated by persons skilled in the art that described active electrode material NaTi
2(PO
4)
3in, Na ︰ Ti ︰ P mol ratio approaches 1 ︰ 2 ︰ 3 as far as possible.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, described calcining heat is between 250～900 ℃, and calcination time is between 6～15 hours.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, described P source compound is at least one in phosphoric acid, phosphorus pentoxide.
Wherein, in said method, the first element M source compound and metalloid element X source compound are to select from cheap compound and other industrial byproduct or waste material.
Wherein, in said method, described carbon-source cpd is DIC, organic carbon, high molecular polymer or natural extract carbon compound, and carbon-source cpd is every mole of carbon weight 1～15g.
Further, described DIC is at least one in conductive black, acetylene carbon black, nano-sized carbon, CNT (carbon nano-tube), Graphene or graphene complex; Described organic carbon is at least one in sucrose, fructose, glucose hexadecanol, carboxylic acid compound malonic acid, adipic acid, acrylic acid, salicylic acid, laurate, ascorbic acid, oleic acid, isocaproic acid or citric acid; Described high molecular polymer carbon compound is at least one in PVOH (PEG), polyvinyl alcohol (PVA), PVOH butyral (PVB), polypropylene, polyvinylpyrrolidone (PUP) or polyacrylic acid; Described natural extract carbon compound is at least one in oleum sojae, cellulose and cellulose derivative thereof, chitin, starch and kerosene.
The invention has the beneficial effects as follows: after the present invention transformed cheap material before this fully, obtain preparing the presoma of active electrode material, redeterminate again each effectively without plain content, and each is effectively prepared burden again without plain content by new mensuration, carry out again next step preparation of electrode material, therefore can utilize cheap compound and other industrial byproduct to prepare active electrode material as raw material, reduce production cost.
The accompanying drawing explanation
The X-ray powder diffraction figure that Fig. 1 is embodiment tri-ferrophosphorus used;
Fig. 2 is the X-ray powder diffraction figure after embodiment tri-ferrophosphorus and alkali metal compound are calcined in air atmosphere;
Fig. 3 be in embodiment tri-ferrophosphorus not in air atmosphere calcining and directly and alkali metal compound calcine the X-ray powder diffraction figure that makes LiFePO4 in oxygen-free atmosphere;
Fig. 4 is the LiFePO4 X-ray powder diffraction figure that embodiment tri-makes;
The X-ray powder diffraction figure that Fig. 5 is the byproduct ferric phosphate of embodiment tetra-from ferrophosphorus is smelted extraction noble metal vanadium cobalt nickel;
Fig. 6 is that embodiment tetra-makes iron phosphate lithium electrode material X-ray powder diffraction figure;
Fig. 7 is that embodiment bis-makes iron manganese phosphate X-ray powder diffraction figure;
Fig. 8 is that embodiment bis-makes iron manganese phosphate for lithium X-ray powder diffraction figure;
Fig. 9 is that embodiment five makes titanium phosphate sodium X-ray powder diffraction figure.
Embodiment
Below by embodiment, the present invention is further described.
The objective of the invention is can overcome active electrode material and prepare the too high shortcoming of expense in order to provide a kind of, utilize cheap compound and other industrial byproduct to prepare the method for active electrode material as raw material.Prepare expense cost in order to reduce active electrode material, the inventor has invented a kind of new method, this method characteristic is raw material and other industrial byproduct or the industrial waste that utilizes low price, through unique process and method, by cheap raw material by refining, after oxidation/reduction processes, change into the presoma that can prepare active electrode material.
Many low price raw material can not directly be used as and prepare the active electrode material presoma, if after the processing method that the words of directly using need to be novel, could allow raw material at a low price change into active electrode material, such as, active electrode material AMPO
4, phosphorus (P) source compound at a low price can be phosphoric acid (H
3pO
4), phosphorus pentoxide (P
2o
5), ferrophosphorus (Fe
xp).M source compound raw material at a low price can be iron (Fe) powder, ferrophosphorus (Fe
xp), manganese (Mn) powder.Ferrophosphorus is the byproduct of phosphorus production, and ferrous sulfate is the byproduct of titanium white production, also has a kind of metallurgical industry, from ferrophosphorus (Fe
xp) refine the byproduct ferric phosphate (Fe after the noble metal such as vanadium cobalt nickel
xpO
4).
As discussed above, in order to produce LiFePO4 and doped iron lithium phosphate isoreactivity electrode material, the industrial production main method is to make Fe source compound with ferrous oxalate at present, ammonium dihydrogen phosphate is made phosphorus source presoma, another method is to make the presoma in source of iron and phosphorus source with meticulous ferric phosphate, the expense of producing ferric phosphate, ferrous oxalate and ammonium dihydrogen phosphate is also quite high, the raw material in the source of iron that price is lower and phosphorus source should be for producing the raw material of ferric phosphate, ammonium dihydrogen phosphate and ferrous oxalate, such as cheap phosphorus source material is phosphoric acid, ferrophosphorus or P
2o
5, cheap ferrous source material is iron powder, the oxide of iron and ferrous sulfate etc.
To use iron powder and ferrophosphorus (Fe in industrial production
xp) etc. the low price raw material are directly produced AFePO
4active electrode material is very difficult, because any residual iron powder and ferrophosphorus can greatly affects the performances such as the capacity of active electrode material and cycle life, with the industry byproducts such as ferrophosphorus production active electrode material AFePO
4not only can reduce price, and reduce the pollution of these byproducts to environment.
The preparation method of active electrode material of the present invention, the molecular formula of active electrode material is A
am
b(XO
4)
cz
d,, wherein M is the first element, and A is the second element, and X is metalloid element, and Z is presoma, the preparation method comprises the steps:
A, with the first element M source compound, metalloid element X source compound and presoma are Z-shaped, become intermediate;
B, measure the first element M and the content of metalloid element X in intermediate, according to A ︰ M ︰ X=1.03～1.1 ︰ 1 ︰ 1 mol ratios, add the second elements A source compound and carbon-source cpd, be made into intermediate blend;
C, ball milling and dry described intermediate blend;
D, in oxygen-free atmosphere the calcining described intermediate blend, obtain active electrode material;
Wherein, described the first element M is at least one in transition metal unit Fe, Mn, V, Co, Ni, Al, Mg, Si, Ca, Sr, Ti, Cd, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ta, W, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;
Described the second elements A is at least one in alkali metal Li, Na or K;
Described metalloid element X is at least one in P, Si, S, Al, Ga, N or V;
Described presoma Z is at least one in OH, F, Cl or Br;
Described a, b and c are greater than zero number, and d is more than or equal to zero number.
The invention provides another kind of execution mode, in said method, described a, b and c are that 1, d is zero, and described metalloid element X is P, and the molecular formula of active electrode material is AMPO
4, so, the preparation method comprises the steps:
A, with P source compound and the first element M source compound, make the phosphate compound;
B, the content of measuring the first element M in the phosphate compound and the content of phosphorus, according to A ︰ M ︰ P=1.03～1.1 ︰ 1 ︰ 1 mol ratios add the second elements A source compound, and carbon-source cpd is made intermediate blend; The weight of carbon-source cpd is 1～30% of intermediate blend weight;
C, ball milling and dry described intermediate blend;
D, in oxygen-free atmosphere the calcining described intermediate blend, obtain active phosphate electrode material AMPO
4.
Preferably, in said method, the phosphate compound is to be prepared by following steps: add reaction in phosphate aqueous solution to make the first mixture the first element M source compound, stir; Splash into aqueous hydrogen peroxide solution and stir in the first mixture after stirring, obtaining the second mixture; Make the phosphate compound with the second mixture.
Wherein, in said method, the second mixture is made phosphate compound method and is: the phosphate compound that centrifugation the second mixture must be wet or centrifugation are also washed phosphate compound that the second mixture gained is wet or phosphate compound that centrifugation, washing dry the second mixture must be done.
Preferably, in said method, the first mixture mixing time is between 0.5～5 hour, and the second mixture mixing time is between 3～15 hours; In phosphate aqueous solution, the weight content of phosphoric acid is 10～50%, and in aqueous hydrogen peroxide solution, the hydrogen peroxide weight content is 5～27%, and the pH value of the first mixture of gained is less than 2.5.
Preferably, in said method, described calcining heat is between 250～900 ℃, and calcination time is between 6～15 hours.
Preferably, in said method, described P source compound is at least one in phosphoric acid, phosphorus pentoxide.
The invention provides another kind of execution mode, in said method, the first element M is Fe, and the molecular formula of active electrode material is AFePO
4, the second elements A source compound is Li
2cO
3, LiOH, Li
2o, Na
2cO
3, NaOH, Na
2o, K
2cO
3, KOH or K
2at least one in O.
Preferably, in said method, the first elemental iron source compound and P source compound are all ferrophosphorus (Fe
xp).
Further preferred, intermediate compound is to be prepared by following steps: with the first elemental iron source compound and P source compound ferrophosphorus and the second elements A source compound, according to mol ratio A ︰ Fe=1.05～1.10 ︰ 1, be mixed to get the first mixture; The first mixture is calcined 2～12 hours under aerobic conditions between 250～600 ℃, and after cool to room temperature, this mixture of ball milling, obtain the second mix powder; Measure the content of iron in the second mix powder, phosphorus and the second elements A, according to A ︰ Fe ︰ P=1.03～1.1 ︰ 1 ︰ 1 mol ratios, prepared burden and add carbon-source cpd, blend together intermediate blend; The weight of carbon-source cpd is 1～30% of intermediate blend weight.
The present invention provides another kind of embodiment again, and in said method, the first element M is Fe, and the second elements A is Li, and the molecular formula of active electrode material is LiFePO
4, described the first element M source compound is at least one in iron powder, ferric oxide powder, ferroferric oxide powder, ferrous sulfate powder or ferric phosphate powder.
Wherein, it will be appreciated by persons skilled in the art that described active electrode material LiFePO
4in, Li ︰ Fe ︰ P mol ratio approaches 1 ︰ 1 ︰ 1 as far as possible.
Ferrous sulfate is the byproduct of titanium white production.Ferric phosphate (Fe
xpO
4) be ferrophosphorus (Fe
xp) refine the byproduct after the noble metal such as vanadium cobalt nickel.
The present invention provides a kind of embodiment again, and in said method, the first element M is Fe and Mn, and the second elements A is Li, and the molecular formula of active electrode material is LiFe
xmn
(1-X)pO
4, the first element M source compound is at least one in iron powder, ferric oxide powder, ferroferric oxide powder, ferrous sulfate powder or ferric phosphate powder, and at least one in manganese powder, manganese dioxide powder.
Wherein, it will be appreciated by persons skilled in the art that described active electrode material LiFe
xmn
(1-X)pO
4in, (Fe+Mn) ︰ P mol ratio approaches 1 ︰ 1 ︰ 1 to Li ︰ as far as possible.
The present invention also provides the preparation method of another kind of active electrode material, and the molecular formula of active electrode material is ATi
2(PO
4)
3, the preparation method comprises the steps:
A, make the compound of Ti oxide and water with the Ti source compound;
In the compound of b, measurement Ti oxide and water, the content of Ti, add A source compound and P source compound according to A ︰ Ti ︰ P=1 ︰ 2 ︰ 3 mol ratios, and carbon-source cpd is made intermediate blend; The weight of carbon-source cpd is 0～30% of intermediate blend weight;
C, ball milling and dry described intermediate blend;
D, in oxygen-free atmosphere the calcining described intermediate blend, obtain active phosphate electrode material ATi
2(PO
4)
3.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, A is Na, and the molecular formula of active electrode material is NaTi
2(PO
4)
3, the Ti source compound is TiO
2, Ti
2(PSO
4)
3, TiOSO
4in at least one.
Wherein, it will be appreciated by persons skilled in the art that described active electrode material NaTi
2(PO
4)
3in, Na ︰ Ti ︰ P mol ratio approaches 1 ︰ 2 ︰ 3 as far as possible.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, described calcining heat is between 250～900 ℃, and calcination time is between 6～15 hours.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, described P source compound is at least one in phosphoric acid, phosphorus pentoxide.
Preferably, in said method, the first element M source compound and metalloid element X source compound are to select from cheap compound and other industrial byproduct or waste material.
Wherein, in said method, described carbon-source cpd is DIC, organic carbon, high molecular polymer or natural extract carbon compound, and carbon-source cpd is every mole of carbon weight 1～15g.
Further, described DIC is at least one in conductive black, acetylene carbon black, nano-sized carbon, CNT (carbon nano-tube), Graphene or graphene complex; Described organic carbon is at least one in sucrose, fructose, glucose hexadecanol, carboxylic acid compound malonic acid, adipic acid, acrylic acid, salicylic acid, laurate, ascorbic acid, oleic acid, isocaproic acid or citric acid; Described high molecular polymer carbon compound is at least one in PVOH (PEG), polyvinyl alcohol (PVA), PVOH butyral (PVB), polypropylene, polyvinylpyrrolidone (PUP) or polyacrylic acid; Described natural extract carbon compound is at least one in oleum sojae, cellulose and cellulose derivative thereof, chitin, starch and kerosene.
Below by embodiment, the specific embodiment of the invention is described further, but therefore protection scope of the present invention is not limited among embodiment.
Embodiment mono-utilizes cheap raw material to prepare active electrode material LiFePO4 LiFePO
4
Make the source of iron raw material with iron powder, phosphoric acid is as phosphorus source raw material, and the procedure for preparing the iron phosphate lithium electrode material is as follows:
Press phosphorus/iron mol ratio 1.1, first prepare concentration 30% phosphate aqueous solution, then iron powder is added to phosphate aqueous solution, after stirring reaction 2 hours, stirring adds 20% aqueous hydrogen peroxide solution, till stirring reaction 8 hours to all iron powders and ferrous ion all disappears, makes ferric phosphate and aqueous mixtures.
The iron powder dissolution velocity is determined by the acidity of solution, course of reaction control pH<2.5.
The centrifugation ferric phosphate, measure the content of phosphorus and iron in wet ferric phosphate, by the Li/Fe/P=1.04/1/1 mol ratio and add 9% weight ratio carbon-source cpd batch mixing, and ball milling, drying, calcination (use temperature of the present invention, lower together) makes the iron phosphate lithium electrode material.
The cheap raw material of embodiment dual-purpose prepare active electrode material LiFePO4 LiFe
0.35mn
0.65pO
4
Make ferrimanganic source raw material with iron powder and manganese powder, phosphoric acid is as phosphorus source raw material, and the procedure for preparing the iron manganese phosphate for lithium electrode material is as follows:
Press phosphorus/iron/manganese mol ratio 1.05/0.35/0.65, first prepare 30% phosphate aqueous solution, again manganese powder, iron powder adds respectively phosphate aqueous solution, and stirring reaction, after 4 hours, stirs and adds 20% aqueous hydrogen peroxide solution, till stirring reaction 10 hours to all manganese powder iron powders and ferrous ion all disappears, make iron manganese phosphate and aqueous mixtures.
Manganese powder iron powder dissolution velocity is determined by the acidity of solution, course of reaction control pH<2.5.
Regulate pH value 4.0-6.0 with ammoniacal liquor, allow all manganese ions all precipitate.
Centrifugation, dry iron manganese phosphate, measure the content of phosphorus in dried iron manganese phosphate, the content of manganese, and the content of iron, by Li/(Fe+Mn)/P=1.05/1/1 mol ratio add 6% weight ratio carbon-source cpd batch mixing, ball milling, drying, calcination makes the iron manganese phosphate for lithium electrode material.
The dried iron manganese phosphate Fe of centrifugation shown in Fig. 7
0.35mn
0.65pO
4x-ray powder diffraction figure.
Make iron manganese phosphate for lithium Fe with above-mentioned iron manganese phosphate shown in Fig. 8
0.35mn
0.65pO
4x-ray powder diffraction figure.
The embodiment tri-use yellow phosphorus industries production byproducts ferrophosphorus powder (FexP) shown in X-ray powder diffraction figure are as shown in Figure 1 made source of iron raw material and phosphorus source raw material, and the procedure for preparing the iron phosphate lithium electrode material is as follows:
1 presses Li/Fe mol ratio 1.07, and lithium P source compound and ferrophosphorus powder mix.
2 said mixtures are put into 300 ℃ of left and right Muffle furnace calcination 8 hours.
Mixture after 3 above-mentioned calcination is cooled to room temperature, pulverizes.Shown in Fig. 2, be to make the X-ray powder diffraction figure of powder after calcination.As Fig. 2 shows, after calcination, the characteristic peak 2THETA=40 of ferrophosphorus powder all disappears.Shown in Fig. 3, be that the ferrophosphorus powder does not have calcination and directly is used for preparing the X-ray powder diffraction figure of LiFePO4 gained powder.As Fig. 3 shows, if without preliminary treatment of the present invention, in the gained LiFePO4, the characteristic peak 2THETA=40 of ferrophosphorus has many residual.
Phosphorus in mix powder after the above-mentioned calcination of 4 mensuration, iron, the content of lithium, and press Li/Fe/P=1.05/1/1 mol ratio batch mixing, and ball milling, drying, the oxygen-free atmosphere calcination makes the iron phosphate lithium electrode material; The LiFePO4 X-ray powder diffraction figure made shown in Fig. 4.
Embodiment tetra-metallurgical industry are from ferrophosphorus (Fe
xp) the byproduct ferric phosphate (Fe after smelting extraction noble metal vanadium cobalt Ni
xpO
4) make source of iron raw material and phosphorus source raw material, the procedure for preparing the iron phosphate lithium electrode material is as follows:
Measure the content of the content iron of phosphorus in above-mentioned ferric phosphate, and by the Li/Fe/P=1.07/1/1 mol ratio and add 6% weight ratio carbon-source cpd batch mixing, ball milling, drying, calcination makes the iron manganese phosphate for lithium electrode material.
Fig. 5 is that metallurgical industry is from ferrophosphorus (Fe
xp) pair product ferric phosphate (Fe after smelting extraction noble metal vanadium cobalt Ni
xpO
4) X-ray powder diffraction figure.
Fig. 6 makes iron phosphate lithium electrode material X-ray powder diffraction figure with ferric phosphate shown in Fig. 5 as presoma.
Embodiment five use NaOH, Ti (SO
4)
2, H
3pO
4. prepare electrode material titanium phosphate sodium NaTi as raw material
2(PO
4)
3procedure as follows:
Be equipped with 1MTi (SO
4)
2the aqueous solution, added thermal agitation 60-120 ℃ after hydrolysis 1-5 hour, centrifugation, washing dry TiO
2hydrate. measure the content of titanium in said mixture, by the Na:Ti:P=1:2:3 mol ratio, above-mentioned raw materials batch mixing in PEG400 is become to pasty mixture; After said mixture is dried, calcination makes electrode material titanium phosphate sodium NaTi
2(PO
4)
3.
Make titanium phosphate sodium NaTi with said method shown in Fig. 9
2(PO
4)
3x-ray powder diffraction figure.
It will be appreciated by persons skilled in the art that except above-mentioned concrete technical scheme and execution mode active electrode material A of the present invention
am
b(XO
4)
cz
dalso include but not limited to following electrode material: Li
0.5vPO4F
0.5; LiVPO
4f; Li
3v
2(PO
4)
2f
3; Li
2mnPO
4f; LiVPO
4cl; LiVPO
4oH; NaVPO
4f; Na
3v
2(PO
4)
2f; Li
2fe
0.5mn
0.5pO
4f; Li
2fePO
4cl; Li
2mnPO
4oH; Li
2fe
0.9mg
0.1pO
4f; Li
2mnPO
4f; Na
3v
2(PO
4)
3; Li
3v
2(PO
4)
3; Li
2fePO
4f; Li
4feMn (SO
4) F
2; Li
3mgFe (SO
4)
3f
2; Li
1.5fe
0.75mn
0.25pO
4f
0.5; Li
1.75mn
0.8mg
0.2pO
4f
0.75; Li
0.6vPO
4f
0.6; Li
0.8vPO
4f
0.8; LiVPO
4f, LiTi
2(PO
4)
3.
Claims (14)
1. the preparation method of active electrode material, the molecular formula of active electrode material is A
am
b(XO
4)
cz
d,, wherein M is the first element, and A is the second element, and X is metalloid element, and Z is presoma, it is characterized in that the preparation method comprises the steps:
A, with the first element M source compound, metalloid element X source compound and presoma are Z-shaped, become intermediate;
B, measure the first element M and the content of metalloid element X in intermediate, according to A ︰ M ︰ X=1.03～1.1 ︰ 1 ︰ 1 mol ratios, add the second elements A source compound and carbon-source cpd, be made into intermediate blend;
C, ball milling and dry described intermediate blend;
D, in oxygen-free atmosphere the calcining described intermediate blend, obtain active electrode material;
Wherein, described the first element M is at least one in transition metal unit Fe, Mn, V, Co, Ni, Al, Mg, Si, Ca, Sr, Ti, Cd, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ta, W, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;
Described the second elements A is at least one in alkali metal Li, Na or K;
Described metalloid element X is at least one in P, Si, S, Al, Ga, N or V;
Described presoma Z is at least one in OH, F, Cl or Br;
Described a, b and c are greater than zero number, and d is more than or equal to zero number.
2. the preparation method of active electrode material according to claim 1 is characterized in that: described a, b and c are that 1, d is zero, and described metalloid element X is P, and the molecular formula of active electrode material is AMPO
4, the preparation method comprises the steps:
A, with P source compound and the first element M source compound, make the phosphate compound;
B, the content of measuring the first element M in the phosphate compound and the content of phosphorus, according to A ︰ M ︰ P=1.03～1.1 ︰ 1 ︰ 1 mol ratios add the second elements A source compound, and carbon-source cpd is made intermediate blend; The weight of carbon-source cpd is 1～30% of intermediate blend weight;
C, ball milling and dry described intermediate blend;
D, in oxygen-free atmosphere the calcining described intermediate blend, obtain active phosphate electrode material AMPO
4.
3. the preparation method of active electrode material according to claim 2, it is characterized in that: the phosphate compound is to be prepared by following steps: add reaction in phosphate aqueous solution to make the first mixture the first element M source compound, stir; Splash into aqueous hydrogen peroxide solution and stir in the first mixture after stirring, obtaining the second mixture; Make the phosphate compound with the second mixture.
4. the preparation method of active electrode material according to claim 3, it is characterized in that: the second mixture is made phosphate compound method and is: the phosphate compound that centrifugation the second mixture must be wet or centrifugation are also washed phosphate compound that the second mixture gained is wet or phosphate compound that centrifugation, washing dry the second mixture must be done.
5. the preparation method of active electrode material according to claim 3, it is characterized in that: the first mixture mixing time is between 0.5～5 hour, and the second mixture mixing time is between 3～15 hours; In phosphate aqueous solution, the weight content of phosphoric acid is 10～50%, and in aqueous hydrogen peroxide solution, the hydrogen peroxide weight content is 5～27%, and the pH value of the first mixture of gained is less than 2.5.
6. the preparation method of active electrode material according to claim 2, it is characterized in that: described calcining heat is between 250～900 ℃, and calcination time is between 6～15 hours.
7. the preparation method of active electrode material according to claim 2, it is characterized in that: described P source compound is at least one in phosphoric acid, phosphorus pentoxide.
8. according to the preparation method of the described active electrode material of any one in claim 1 to 6, it is characterized in that: the first element M is Fe, and the molecular formula of active electrode material is AFePO
4, the second elements A source compound is Li
2cO
3, LiOH, Li
2o, Na
2cO
3, NaOH, Na
2o, K
2cO
3, KOH or K
2at least one in O.
9. the preparation method of active electrode material according to claim 8, it is characterized in that: the first elemental iron source compound and P source compound are all ferrophosphorus.
10. the preparation method of active electrode material according to claim 9 is characterized in that intermediate compound is to be prepared by following steps: with the first elemental iron source compound and P source compound ferrophosphorus and the second elements A source compound, according to mol ratio A ︰ Fe=1.05～1.10 ︰ 1, be mixed to get the first mixture; The first mixture is calcined 2～12 hours under aerobic conditions between 250～600 ℃, and after cool to room temperature, this mixture of ball milling, obtain the second mix powder; Measure the content of iron in the second mix powder, phosphorus and the second elements A, according to A ︰ Fe ︰ P=1.03～1.1 ︰ 1 ︰ 1 mol ratios, prepared burden and add carbon-source cpd, blend together intermediate blend; The weight of carbon-source cpd is 1～30% of intermediate blend weight.
11. the preparation method according to the described active electrode material of any one in claim 1 to 7 is characterized in that: the first element M is Fe, the second elements A is Li, and the molecular formula of active electrode material is LiFePO
4, described the first element M source compound is at least one in iron powder, ferric oxide powder, ferroferric oxide powder, ferrous sulfate powder or ferric phosphate powder.
12. the preparation method according to the described active electrode material of any one in claim 1 to 7 is characterized in that: the first element M is Fe and Mn, and the second elements A is Li, and the molecular formula of active electrode material is LiFe
xmn
(1-X)pO
4, the first element M source compound is at least one in iron powder, ferric oxide powder, ferroferric oxide powder, ferrous sulfate powder or ferric phosphate powder, and at least one in manganese powder, manganese dioxide powder.
13. the preparation method of active electrode material, the molecular formula of active electrode material is ATi
2(PO
4)
3, it is characterized in that the preparation method comprises the steps:
A, make the compound of Ti oxide and water with the Ti source compound;
In the compound of b, measurement Ti oxide and water, the content of Ti, add A source compound and P source compound according to A ︰ Ti ︰ P=1 ︰ 2 ︰ 3 mol ratios, and carbon-source cpd is made intermediate blend; The weight of carbon-source cpd is 0～30% of intermediate blend weight;
C, ball milling and dry described intermediate blend;
D, in oxygen-free atmosphere the calcining described intermediate blend, obtain active phosphate electrode material ATi
2(PO
4)
3.
14. the preparation method according to the described active electrode material of any one in claim 1 to 13 is characterized in that: the first element M source compound and metalloid element X source compound are to select from cheap compound and other industrial byproduct or waste material.
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