CN103456954B - The preparation method of active electrode material - Google Patents
The preparation method of active electrode material Download PDFInfo
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- CN103456954B CN103456954B CN201310403393.6A CN201310403393A CN103456954B CN 103456954 B CN103456954 B CN 103456954B CN 201310403393 A CN201310403393 A CN 201310403393A CN 103456954 B CN103456954 B CN 103456954B
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Abstract
The invention discloses a kind of method preparing active electrode material with cheap raw material, belong to active electrode material field.In active electrode material, M is the first element, and A is the second element, and X is metalloid element, and Z is presoma, and preparation method is as follows: a, with the first element M source compound, metalloid element X source compound and presoma Z-shaped become intermediate; B, measure the first element M and the content of metalloid element X in intermediate, add the second elements A source compound and carbon-source cpd according to certain mol proportion, be made into intermediate blend, ball milling and drying; C, calcine described intermediate blend in an oxygen-free atmosphere, obtain active electrode material.Cheap material transformed and obtained precursor by the present invention before this completely, and the new content measuring each effective nothing element, again prepare burden, then carry out next step preparation of electrode material, the present invention can utilize cheap compound or byproduct to make raw material, reduces production cost.
Description
Technical field
The invention belongs to active electrode material field, particularly a kind of method preparing active electrode material with cheap raw material.
Background technology
Lead-acid battery is the most traditional rechargeable battery, has and reaches 150 years applicating histories, uses because it manufactures simply cheap always.Lead-acid battery energy density is low, and cycle life is short, the defects such as the murder by poisoning of environment has been not suitable for 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 feature such as good, can be used as electrokinetic cell.But because the electrode material of lithium ion battery and battery preparation cost remain high, be difficult at present in marketing, replace cheap lead-acid battery.
, because its electrode material and manufacturing cost are all very low, cycle performance is more excellent than lead-acid battery for the deionized water solution battery AIB (aqueous ion battery) of nearest development, gets a good chance of replacing the lead-acid battery of poisoning environment in the near future.Though deionized water solution battery AIB environmental protection, energy density the same as lead-acid battery is low and can only be used for energy-storage battery, cannot be applied in high power high power capacity electrokinetic cell field.
How preparing at a low price lithium ion battery electrode material, reduce lithium ion battery manufacturing cost, is one of the key factor that can commercially promote of lithium ion battery.
The present invention is that relation prepares cheap electrode material, from the cheapest raw material of price, through process and the method for uniqueness, prepares cheap electrode material.
Industry preparation lithium iron phosphate electrode material, traditional production technology is that ferrous oxalate is as source of iron raw material, ammonium dihydrogen phosphate is as phosphorus source raw material, two manufacture of materials produce cost, production process releases environmentally harmful gas, the production technology more and more accounting for main flow at present makes source of iron and phosphorus source raw material with ferric phosphate, and ferric phosphate is produced and also produced cost.
Preparation lithium iron phosphate electrode material, cheap P source compound is phosphoric acid or phosphorus pentoxide, and cheap ferrous source material is iron powder, or the byproduct of other industry such as ferrous sulfate (titanium dioxide industry production byproduct), such as ferrophosphorus (Fe
xp, yellow phosphorus industry produces byproduct), such as smelt the byproduct ferric phosphate (Fe after extracting noble metal vanadium cobalt nickel from ferrophosphorus
xpO
4).
Prepare phosphate compound electrode material, cheap P source compound is phosphoric acid or phosphorus pentoxide, and cheap Ti source compound is TiOSO
4with 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, one of reason sometimes, and raw material transform completely not have effective method to ensure, the unconverted Magnetic Materials of minute quantity may be very large to the performance impact of electrode material.Reason two, there is certain change in the proportioning of each element, if do next step preparation by proportioning before conversion, certainly will cause mixing ratio error, affect the performance of electrode material in conversion process.
The inventive method, after above-mentioned cheap material is transformed completely, redeterminates each effective content without element, and again prepares burden by the new content measuring each effective nothing element, then carries out next step preparation of electrode material.
Summary of the invention
The object of this invention is to provide and a kind ofly can overcome active electrode material and prepare the too high shortcoming of expense, the byproduct of cheap compound and other industry can be utilized as raw material to prepare the method for active electrode material.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of active electrode material, and 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, and preparation method comprises the steps:
A, with the first element M source compound, metalloid element X source compound and presoma Z-shaped become intermediate;
B, measure the first element M and the content of metalloid element X in intermediate, add the second elements A source compound and carbon-source cpd according to A ︰ M ︰ X=1.03 ~ 1.1 ︰ 1 ︰ 1 mol ratio, be made into intermediate blend;
Intermediate blend described in c, ball milling and drying;
D, calcine described intermediate blend in an oxygen-free atmosphere, obtain active electrode material;
Wherein, described 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 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 be greater than zero number, d be more than or equal to zero number.
Wherein, described a, b and c are 1, d is zero, and described metalloid element X is P, and the molecular formula of active electrode material is AMPO
4, preparation method comprises the steps:
A, obtain phosphate complex with P source compound and the first element M source compound;
The content of the first element M and the content of phosphorus in b, measurement phosphate complex, add the second elements A source compound, and carbon-source cpd makes intermediate blend according to A ︰ M ︰ P=1.03 ~ 1.1 ︰ 1 ︰ 1 mol ratio; The weight of carbon-source cpd is 1 ~ 30% of intermediate blend weight;
Intermediate blend described in c, ball milling and drying;
D, calcine described intermediate blend in an oxygen-free atmosphere, obtain active phosphate electrode material AMPO
4.
Wherein, in said method, phosphate complex is prepared by following steps: the first element M source compound is added reaction in phosphate aqueous solution and make the first mixture, stir; In the first mixture after stirring, instill aqueous hydrogen peroxide solution and stir, obtaining the second mixture; Phosphate complex is made with the second mixture.
Wherein, in said method, the second mixture is made phosphate complex method and is: the phosphate complex that centrifugation second mixture must wet or centrifugation and wash phosphate complex that the second mixture gained wets or centrifugation, phosphate complex that washing dry 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, 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 DEG C, 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 prepared by following steps: be mixed to get the first mixture 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; First mixture is calcined 2 ~ 12 hours under aerobic conditions between 250 ~ 600 DEG C, and after cool to room temperature, this mixture of ball milling, obtains the second mix powder; Measure the content of iron in the second mix powder, phosphorus and the second elements A, carry out preparing burden and adding carbon-source cpd according to A ︰ Fe ︰ P=1.03 ~ 1.1 ︰ 1 ︰ 1 mol ratio, namely 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, the first described 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 is as far as possible close to 1 ︰ 1 ︰ 1.
Ferrous sulfate is the byproduct of titanium white production.Ferric phosphate (Fe
xpO
4) be ferrophosphorus (Fe
xp) byproduct after the noble metals such as vanadium cobalt nickel is refined.
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 manganese powder, at least one in manganese dioxide powder.
Wherein, described active electrode material LiFe
xmn
(1-X)pO
4in, (Fe+Mn) ︰ P mol ratio is as far as possible close to 1 ︰ 1 ︰ 1 for Li ︰.
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, preparation method comprises the steps:
A, obtain the compound of Ti oxide and water with 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, and carbon-source cpd makes intermediate blend according to A ︰ Ti ︰ P=1 ︰ 2 ︰ 3 mol ratio; The weight of carbon-source cpd is 0 ~ 30% of intermediate blend weight;
Intermediate blend described in c, ball milling and drying;
D, calcine described intermediate blend in an oxygen-free atmosphere, obtain active phosphate electrode material ATi
2(PO
4)
3.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, 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, 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 is as far as possible close to 1 ︰ 2 ︰ 3.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, described calcining heat is between 250 ~ 900 DEG C, 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 select from the byproduct or waste material of cheap compound and other industry.
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, chitin, starch and kerosene.
The invention has the beneficial effects as follows: after cheap material transforms by the present invention before this completely, obtain the presoma can preparing active electrode material, redeterminate each effective content without element again, and again prepare burden by the new content measuring each effective nothing element, carry out next step preparation of electrode material again, therefore the byproduct of cheap compound and other industry can be utilized to prepare active electrode material as raw material, reduce production cost.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction figure of embodiment three ferrophosphorus used;
Fig. 2 is the X-ray powder diffraction figure after embodiment three ferrophosphorus and alkali metal compound are calcined in air atmosphere;
Fig. 3 be in embodiment three ferrophosphorus not in air atmosphere calcining and directly and alkali metal compound calcine the X-ray powder diffraction figure of obtained LiFePO4 in an oxygen-free atmosphere;
Fig. 4 is the LiFePO4 X-ray powder diffraction figure that embodiment three obtains;
Fig. 5 is that embodiment four smelts the X-ray powder diffraction figure of the byproduct ferric phosphate after extracting noble metal vanadium cobalt nickel from ferrophosphorus;
Fig. 6 is that embodiment four obtains lithium iron phosphate electrode material X-ray powder diffraction figure;
Fig. 7 is that embodiment two obtains iron manganese phosphate X-ray powder diffraction figure;
Fig. 8 is that embodiment two obtains iron manganese phosphate for lithium X-ray powder diffraction figure;
Fig. 9 is that embodiment five obtains titanium phosphate sodium X-ray powder diffraction figure.
Embodiment
Below by embodiment, the present invention is further described.
The object of the invention is can overcome active electrode material prepare the too high shortcoming of expense to provide a kind of, utilize the byproduct of cheap compound and other industry to prepare the method for active electrode material as raw material.Expense cost is prepared in order to reduce active electrode material, the present inventor has invented a kind of new method, this method characteristic utilizes the raw material of low price and the byproduct of other industry or industrial waste, through unique process and method, by cheap raw material by refining, after oxidation/reduction process, change into the presoma can preparing active electrode material.
Many low price raw material can not directly as preparing active electrode material presoma, if to directly use need novel processing method after raw material at a low price could be allowed to 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) the byproduct ferric phosphate (Fe after the noble metals such as vanadium cobalt nickel is refined
xpO
4).
As discussed above, in order to produce LiFePO4 and doped iron lithium phosphate isoreactivity electrode material, current industrial production main method makes Fe source compound with ferrous oxalate, phosphorus source presoma made by ammonium dihydrogen phosphate, another method makes the presoma in source of iron and phosphorus source, 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 used to the raw material producing 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.
With iron powder and ferrophosphorus (Fe in industrial production
xetc. P) raw material directly produce AFePO at a low price
4active electrode material is very difficult, because the performance such as the capacity of any residual iron powder and ferrophosphorus meeting extreme influence active electrode material and cycle life, produces active electrode material AFePO with industry byproducts such as ferrophosphorus
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, and preparation method comprises the steps:
A, with the first element M source compound, metalloid element X source compound and presoma Z-shaped become intermediate;
B, measure the first element M and the content of metalloid element X in intermediate, add the second elements A source compound and carbon-source cpd according to A ︰ M ︰ X=1.03 ~ 1.1 ︰ 1 ︰ 1 mol ratio, be made into intermediate blend;
Intermediate blend described in c, ball milling and drying;
D, calcine described intermediate blend in an oxygen-free atmosphere, obtain active electrode material;
Wherein, described 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 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 be greater than zero number, d be more than or equal to zero number.
The invention provides another kind of execution mode, in said method, described a, b and c are 1, d is zero, and described metalloid element X is P, and the molecular formula of active electrode material is AMPO
4, so, namely preparation method comprises the steps:
A, obtain phosphate complex with P source compound and the first element M source compound;
The content of the first element M and the content of phosphorus in b, measurement phosphate complex, add the second elements A source compound, and carbon-source cpd makes intermediate blend according to A ︰ M ︰ P=1.03 ~ 1.1 ︰ 1 ︰ 1 mol ratio; The weight of carbon-source cpd is 1 ~ 30% of intermediate blend weight;
Intermediate blend described in c, ball milling and drying;
D, calcine described intermediate blend in an oxygen-free atmosphere, obtain active phosphate electrode material AMPO
4.
Preferably, in said method, phosphate complex is prepared by following steps: the first element M source compound is added reaction in phosphate aqueous solution and make the first mixture, stir; In the first mixture after stirring, instill aqueous hydrogen peroxide solution and stir, obtaining the second mixture; Phosphate complex is made with the second mixture.
Wherein, in said method, the second mixture is made phosphate complex method and is: the phosphate complex that centrifugation second mixture must wet or centrifugation and wash phosphate complex that the second mixture gained wets or centrifugation, phosphate complex that washing dry 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, 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 DEG C, 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 prepared by following steps: be mixed to get the first mixture 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; First mixture is calcined 2 ~ 12 hours under aerobic conditions between 250 ~ 600 DEG C, and after cool to room temperature, this mixture of ball milling, obtains the second mix powder; Measure the content of iron in the second mix powder, phosphorus and the second elements A, carry out preparing burden and adding carbon-source cpd according to A ︰ Fe ︰ P=1.03 ~ 1.1 ︰ 1 ︰ 1 mol ratio, namely blend together intermediate blend; The weight of carbon-source cpd is 1 ~ 30% of intermediate blend weight.
The present invention reoffers another kind of embodiment, 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, the first described 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 is as far as possible close to 1 ︰ 1 ︰ 1.
Ferrous sulfate is the byproduct of titanium white production.Ferric phosphate (Fe
xpO
4) be ferrophosphorus (Fe
xp) byproduct after the noble metals such as vanadium cobalt nickel is refined.
The present invention reoffers a kind of embodiment, 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 manganese powder, at least one in 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 is as far as possible close to 1 ︰ 1 ︰ 1 for Li ︰.
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, preparation method comprises the steps:
A, obtain the compound of Ti oxide and water with 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, and carbon-source cpd makes intermediate blend according to A ︰ Ti ︰ P=1 ︰ 2 ︰ 3 mol ratio; The weight of carbon-source cpd is 0 ~ 30% of intermediate blend weight;
Intermediate blend described in c, ball milling and drying;
D, calcine described intermediate blend in an oxygen-free atmosphere, 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, 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 is as far as possible close to 1 ︰ 2 ︰ 3.
Wherein, above-mentioned preparation ATi
2(PO
4)
3in method, described calcining heat is between 250 ~ 900 DEG C, 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 select from the byproduct or waste material of cheap compound and other industry.
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, chitin, starch and kerosene.
Below by embodiment, the specific embodiment of the invention is described further, but not therefore by protection scope of the present invention restriction in one embodiment.
Embodiment one utilizes cheap raw material to prepare active electrode material LiFePO4 LiFePO
4
Make source of iron raw material with iron powder, phosphoric acid is as phosphorus source raw material, and the procedure of preparation lithium iron phosphate electrode material is as follows:
By phosphorus/iron mol ratio 1.1, first prepare concentration 30% phosphate aqueous solution, then iron powder is added phosphate aqueous solution, stirring reaction is after 2 hours, stirring adds 20% aqueous hydrogen peroxide solution, and stirring reaction 8 is little till all iron powders and ferrous ion all disappear, obtained ferric phosphate and aqueous mixtures.
Iron powder dissolution velocity is determined by the acidity of solution, course of reaction control pH<2.5.
Centrifugation ferric phosphate, measures the content of phosphorus and iron in wet ferric phosphate, adds 9% weight ratio carbon-source cpd batch mixing, ball milling by Li/Fe/P=1.04/1/1 mol ratio, dry, calcination (use temperature of the present invention, lower with) obtained lithium iron phosphate electrode material.
Active electrode material LiFePO4 LiFe prepared by the cheap raw material of embodiment dual-purpose
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 preparing iron manganese phosphate for lithium electrode material is as follows:
By phosphorus/iron/manganese mol ratio 1.05/0.35/0.65, first prepare 30% phosphate aqueous solution, again manganese powder, iron powder adds phosphate aqueous solution respectively, and stirring reaction, after 4 hours, stirs and adds 20% aqueous hydrogen peroxide solution, stirring reaction 10 is little till all manganese powder iron powders and ferrous ion all disappear, obtained 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.
With ammoniacal liquor adjust ph 4.0-6.0, all manganese ions are allowed all to precipitate.
Centrifugation, dry iron manganese phosphate, measures 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, dry, calcination obtains 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.
Iron manganese phosphate for lithium Fe is obtained with above-mentioned iron manganese phosphate shown in Fig. 8
0.35mn
0.65pO
4x-ray powder diffraction figure.
Embodiment three is produced the ferrophosphorus powder (FexP) of byproduct as shown in Figure 1 shown in X-ray powder diffraction figure with yellow phosphorus industry and is made source of iron raw material and phosphorus source raw material, and the procedure of preparation lithium iron phosphate 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 put into about 300 DEG C Muffle furnace calcination 8 hours.
Mixture after 3 above-mentioned calcination is cooled to room temperature, pulverizes.The X-ray powder diffraction figure of obtained powder after calcination shown in Fig. 2.As Fig. 2 shows, after calcination, the characteristic peak 2THETA=40 of ferrophosphorus powder all disappears.That ferrophosphorus powder does not have calcination and is directly used for preparing the X-ray powder diffraction figure of LiFePO4 gained powder shown in Fig. 3.As Fig. 3 shows, if without preliminary treatment of the present invention, in 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, ball milling, dry, oxygen-free atmosphere calcination obtains lithium iron phosphate electrode material; LiFePO4 X-ray powder diffraction figure obtained shown in Fig. 4.
Embodiment four metallurgical industry is from ferrophosphorus (Fe
xp) the byproduct ferric phosphate (Fe after extracting noble metal vanadium cobalt Ni is smelted
xpO
4) make source of iron raw material and phosphorus source raw material, the procedure of preparation lithium iron phosphate electrode material is as follows:
Measure the content of the content iron of phosphorus in above-mentioned ferric phosphate, and add 6% weight ratio carbon-source cpd batch mixing, ball milling by Li/Fe/P=1.07/1/1 mol ratio, dry, calcination obtains iron manganese phosphate for lithium electrode material.
Fig. 5 is that metallurgical industry is from ferrophosphorus (Fe
xp) pair product ferric phosphate (Fe after extracting noble metal vanadium cobalt Ni is smelted
xpO
4) X-ray powder diffraction figure.
Ferric phosphate shown in Fig. 6 Fig. 5 obtains lithium iron phosphate electrode material X-ray powder diffraction figure as presoma.
Embodiment five 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, adds thermal agitation 60-120 DEG C after hydrolysis 1-5 hour, centrifugation, washing dry TiO
2hydrate. measure the content of titanium in said mixture, by Na:Ti:P=1:2:3 mol ratio, above-mentioned raw materials batch mixing in PEG400 is become pasty mixture; After said mixture is dried, calcination obtains electrode material titanium phosphate sodium NaTi
2(PO
4)
3.
The shown said method of Fig. 9 obtains titanium phosphate sodium NaTi
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 cycle unit material is included but not limited to: 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 (2)
1. the preparation method of active electrode material, the molecular formula of active electrode material is AFePO
4, wherein Fe is the first element, and A is the second element, it is characterized in that preparation method comprises the steps:
A, be mixed to get the first mixture 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; First mixture is calcined 2 ~ 12 hours under aerobic conditions between 250 ~ 600 DEG C, and after cool to room temperature, this mixture of ball milling, obtains the second mix powder; Measure the content of iron in the second mix powder, phosphorus and the second elements A, carry out preparing burden and adding carbon-source cpd according to A ︰ Fe ︰ P=1.03 ~ 1.1 ︰ 1 ︰ 1 mol ratio, namely blend together intermediate blend; The weight of carbon-source cpd is 1 ~ 30% of intermediate blend weight;
Intermediate blend described in b, ball milling and drying;
C, calcine described intermediate blend in an oxygen-free atmosphere, obtain active electrode material;
Wherein, described second elements A is at least one in alkali metal Li, Na or K, and 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;
First elemental iron source compound and P source compound are all ferrophosphorus.
2. the preparation method of active electrode material according to claim 1, is characterized in that: in oxygen-free atmosphere, calcining heat is between 250 ~ 900 DEG C, and calcination time is between 6 ~ 15 hours.
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| CN105084330A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院物理研究所 | Ferromagnetic semiconductor material Li (Cd, Mn) P and preparation method thereof |
| CN104409732A (en) * | 2014-12-11 | 2015-03-11 | 上海宝钢磁业有限公司 | Preparation method for lithium iron phosphate material by adopting mixed iron source |
| CN104934587B (en) * | 2015-04-07 | 2018-08-14 | 黄桂清 | The method for preparing new energy battery-active electrode material using ilmenite traditional handicraft |
| CN105336947A (en) * | 2015-07-23 | 2016-02-17 | 浙江大学 | Lithium manganese phosphate chloride electrode material and preparation method thereof |
| CN105244503A (en) * | 2015-11-13 | 2016-01-13 | 武汉大学 | Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material |
| CN106315683A (en) * | 2016-08-22 | 2017-01-11 | 武汉科技大学 | Method for preparing manganese ferrite by using waste zinc manganese dry cell as manganese source |
| CN109638274B (en) * | 2018-12-14 | 2022-03-11 | 廊坊绿色工业技术服务中心 | Molybdenum-ytterbium co-doped sodium iron silicate composite electrode material and preparation method thereof |
| 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 |
| CN117430134B (en) * | 2023-12-21 | 2024-04-05 | 山东海化集团有限公司 | Preparation method of ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974410A (en) * | 2006-12-19 | 2007-06-06 | 中南大学 | Process of producing lithium iron phosphate precursor with ferrous sulfate as side product of titanium white production |
| CN101154745A (en) * | 2007-09-20 | 2008-04-02 | 复旦大学 | Hydrographical rechargeable lithium or sodium ion battery |
| CN101219783A (en) * | 2008-01-23 | 2008-07-16 | 四川大学 | Method for producing electrode material with ferrophosphorus |
| CN101807696A (en) * | 2010-04-12 | 2010-08-18 | 浙江大学 | Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof |
| CN101820062A (en) * | 2010-05-05 | 2010-09-01 | 黄铭 | Multi-solvent preparation method of lithium iron phosphate |
| CN102255078A (en) * | 2011-05-27 | 2011-11-23 | 丁建民 | Coordinated method for preparing nanometer spherical iron phosphate and then using carbon fusion method to prepare nanometer spherical lithium iron phosphate |
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|---|---|---|---|---|
| JP2013084449A (en) * | 2011-10-11 | 2013-05-09 | Fuji Heavy Ind Ltd | Positive electrode active material, lithium ion secondary battery including the same, and method for producing positive electrode active material |
-
2013
- 2013-09-06 CN CN201310403393.6A patent/CN103456954B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974410A (en) * | 2006-12-19 | 2007-06-06 | 中南大学 | Process of producing lithium iron phosphate precursor with ferrous sulfate as side product of titanium white production |
| CN101154745A (en) * | 2007-09-20 | 2008-04-02 | 复旦大学 | Hydrographical rechargeable lithium or sodium ion battery |
| CN101219783A (en) * | 2008-01-23 | 2008-07-16 | 四川大学 | Method for producing electrode material with ferrophosphorus |
| CN101807696A (en) * | 2010-04-12 | 2010-08-18 | 浙江大学 | Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof |
| CN101820062A (en) * | 2010-05-05 | 2010-09-01 | 黄铭 | Multi-solvent preparation method of lithium iron phosphate |
| CN102255078A (en) * | 2011-05-27 | 2011-11-23 | 丁建民 | Coordinated method for preparing nanometer spherical iron phosphate and then using carbon fusion method to prepare nanometer spherical lithium iron phosphate |
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