CN104817059A - Method for preparing battery-grade iron phosphate from reaction between iron powder and phosphoric acid - Google Patents
Method for preparing battery-grade iron phosphate from reaction between iron powder and phosphoric acid Download PDFInfo
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- CN104817059A CN104817059A CN201510209131.5A CN201510209131A CN104817059A CN 104817059 A CN104817059 A CN 104817059A CN 201510209131 A CN201510209131 A CN 201510209131A CN 104817059 A CN104817059 A CN 104817059A
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Abstract
The invention discloses a method for preparing a battery-grade iron phosphate from a reaction between iron powder and phosphoric acid. The method comprises the following steps: mixing the iron powder with dilute phosphoric acid for generating Fe(H2PO4)2 by reaction, then adding oxidizing agent therein for generating iron phosphate precipitation through oxidation; obtaining the highly pure battery-grade iron phosphate, i.e., iron phosphate dihydrate. The iron phosphate dihydrate is a nanometer flake-like crystal of metastrengite (phosphosiderite) crystal form. The method for preparing the battery-grade iron phosphate from the reaction between the iron powder and the phosphoric acid is simple in technology and convenient to operate, without other impurity ions being introduced. The filter liquor and the cleaning solution can be reused, accordingly waste material and wastewater are not generated, and the cost is low. Therefore, the method for preparing the battery-grade iron phosphate from the reaction between the iron powder and the phosphoric acid is an environment-friendly green technology. The prepared iron phosphate is the highly pure flake-like iron phosphate crystal that can be used as a raw material for the anode material lithium iron phosphate of a lithium ion battery.
Description
Technical field
The invention belongs to technical field of inorganic, relate to a kind of preparation method of lithium ion battery anode material lithium iron phosphate presoma, particularly a kind of preparation method being prepared ferric lithium phosphate precursor tertiary iron phosphate by iron powder and phosphatase reaction.
Background technology
Tertiary iron phosphate can be used as the source of iron preparing lithium ion battery anode material lithium iron phosphate, compared to other two kinds of conventional source of iron-Ferroxs and ferric oxide, tertiary iron phosphate is utilized to do the high temperature solid-state method technique of raw material simple, easily realize automatic flow to control, the iron lithium phosphate specific storage particularly produced is high, processing characteristics is superior, the stabilization between easily realizing batch.Therefore, tertiary iron phosphate has the application prospect more wide than other two kinds of sources of iron.
Although tertiary iron phosphate technique prepares the first-selected technique of iron lithium phosphate on a large scale, its cost is higher, and only tertiary iron phosphate just accounts for nearly half of raw materials cost, significantly must reduce the cost of tertiary iron phosphate, meet the need of market with high performance-price ratio.From disclosed patent, tertiary iron phosphate many employings divalence or trivalent iron salt and phosphoric acid or phosphate reaction and obtain, the most frequently used molysite is ferrous sulfate, iron(ic) chloride or iron nitrate, and this inevitably will introduce impurity anions in product tertiary iron phosphate; In addition, take phosphoric acid salt as precipitation agent, and in order to regulate the pH value of reaction soln to commonly use ammoniacal liquor, sodium hydroxide or potassium hydroxide, also can introduce impurity cationic in the product.Because foreign ion can occur when battery charge or discharge, to the power of battery and the harmful redox reaction of cycle performance, to cause the high tertiary iron phosphate of foreign ion level to be not suitable as the raw material preparing iron lithium phosphate.In order to obtain conforming with the tertiary iron phosphate preparing iron lithium phosphate requirement, require to use a large amount of deionized waters to wash intermediate product or finished product, this adds the production cost of tertiary iron phosphate undoubtedly, creates a large amount of trade effluent simultaneously, as dealt with improperly, will work the mischief to environment.
Patent CN102333725B describes a kind of preparation method of tertiary iron phosphate, in described method by the oxidation state being selected from oxyhydroxide, oxide compound, oxyhydroxide, hydrous oxide, carbonate and hydroxyl carbonate be iron (II), iron (III) or mixing iron (II, III) compound and iron powder are introduced in the aqueous medium of phosphoric acid, Fe
2+ion-solubility, Fe
3+fe is obtained by reacting with iron powder
2+, after removing insoluble composition after filtration, oxygenant is added phosphoric acid water-based Fe
2+with the iron (II) in oxidizing solution in solution, obtain tertiary iron phosphate precipitation.The advantage of the method is, can prepare highly purified tertiary iron phosphate compared with common method, and follow-uply need not carry out the especially complicated and washing process of costliness.But, described method iron cpd used otherwise because digestion time is long not easily with phosphatase reaction, or itself is unstable and not easily preserve, thus requires from the fresh preparation of other molysite.Though the iron cpd of these fresh preparations is through repetitive scrubbing, still inevitably introduce other impurity anions, if be the initial iron material preparing high-purity phosphoric acid iron with it, treating processes is still loaded down with trivial details.
Patent CN102897739A, CN103058160A describe the method preparing low-cost cell-grade iron phosphate material based on iron powder corrosion, described method is initial iron material with zeroth order source of iron, generate hydrous iron oxide with organic corrosion acid or the starch reaction be under alkaline condition, then obtain tertiary iron phosphate with phosphatase reaction.Although the method take iron powder as raw material reduce production cost, in production process, use other inorganic or organic matter raw material, still needed repetitive scrubbing to remove these reactants, otherwise be difficult to obtain battery-grade iron phosphate; Moreover many, the consuming time length of described method steps, as the reaction of reduced iron powder, starch and bicarbonate of ammonia need 60 DEG C of water-bath arrest reactions 80 hours, this both needed lot of energy, also obviously can reduce the industrial output of product because of length consuming time.
Patent CN102051630B discloses a kind of method of preparing superfine iron phosphate through electrolytic, described method is in plate and frame electrolyzer, with phosphoric acid or aqueous phosphatic for electrolytic solution, with iron or iron containing alloy for anode, graphite rod, copper, iron or iron alloy are negative electrode, and electrolytic synthesis ferrous phosphate adds oxygenant and is oxidized to tertiary iron phosphate, by sedimentation and filtration, washing, drying, obtained superfine iron phosphate powder.Although the method makes full use of cheap iron or iron alloy reduces production cost as source of iron, needing to consume a large amount of electric energy, because using phosphate solution electrolytic solution, many impurity cationics can be mingled with, as K in the tertiary iron phosphate of synthesis
+, Na
+, NH
4 +ions etc., for removing these ions as far as possible, still need to use a large amount of deionized water to wash, this can increase production cost unavoidably.
Being no matter the traditional technology of raw material with molysite, or avoiding the tertiary iron phosphate preparation technology that uses the molysite of impure negatively charged ion to be raw material above, still there is such or such deficiency in its preparation process.Therefore, need to find one thoroughly can avoid foreign ion and other inorganic or organic impact, the Green production method of the high purity battery level tertiary iron phosphate of energy-saving and environmental protection simultaneously, low cost.
Summary of the invention
Object of the present invention is exactly the defect in order to overcome prior art, provides a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction of low cost.
For this reason, the present invention by the following technical solutions: mixed with certain density phosphoric acid by iron powder, reaction generates Fe (H
2pO
4)
2, then add hydrogen peroxide oxidation generate tertiary iron phosphate precipitation, after filtration, washing and drying obtain high purity battery level tertiary iron phosphate.
The chemical equation of the principal reaction related in process is as shown in (I), (II):
Fe + 2H
3PO
4＝ Fe(H
2PO
4)
2+ H
2↑ （Ⅰ）
Fe(H
2PO
4)
2+ 0.5H
2O
2+ H
2O ＝ FePO
4·2H
2O + H
3PO
4（Ⅱ）
On the basis adopting technique scheme, the present invention also can adopt following further technical scheme, and it comprises the following steps:
(1) in room temperature or higher than under the condition of room temperature, the iron powder of order number more than 200 orders is dissolved in dilute phosphoric acid, the mass percentage concentration of dilute phosphoric acid controls 15 ~ 45%, and iron powder controls at 1 ︰ 2 ~ 4 with the ratio of the amount of substance of phosphoric acid, until iron powder dissolves completely generate Fe (H
2pO
4)
2, solution becomes blackish green, leaves residuum and insoluble black solid impurity in dissolution process;
(2) by insoluble black solid impurity from Fe (H
2pO
4)
2remove after filtration in solution, obtain the green solution clarified;
(3), at the temperature more than 70 DEG C, crystallization Iron phosphate dihydrate is obtained with the ferrous salt in oxidizing green solution; Before oxidizing reaction occurring, carrying out regulator solution volume by adding water, thus controlling the pH value of reaction soln, pH controls 0.5 ~ 1.8, adds water and is preferably distilled water;
(4) by the ageing under room temperature of crystallization Iron phosphate dihydrate, carry out afterwards filtering, washing and drying, obtain baby pink product and Iron phosphate dihydrate; Iron phosphate dihydrate is the nano-sheet crystal of metastrengite (kakoxene) crystal formation;
Recycling of filtrate and washings: after filtrate and washings being merged, namely can be used as dilute phosphoric acid recycle toward wherein adding suitable phosphoric acid.
The non-limitative example of iron powder comprises reduced iron powder, the electrolytic iron powder of weight of iron percentage composition >=99%, the spheroidal graphite cast iron powder one of weight of iron percentage composition >=97% of weight of iron percentage composition >=98% or appoints both and three's mixture.
The non-limitative example of oxygenant comprises hydrogen peroxide, ozone or both are used in combination.
The order number of iron powder is 200 ~ 1000 orders; Be preferably 300 ~ 500 orders.
The mass percentage concentration of dilute phosphoric acid controls 25 ~ 35%;
Iron powder and the ratio of the amount of substance of phosphoric acid control at 1 ︰ 2.5 ~ 3;
Iron powder is dissolved in temperature of reaction in dilute phosphoric acid and controls at 20 ~ 60 DEG C, and preferable reaction temperature controls at 40 ~ 50 DEG C.
The pH of controlled oxidization reaction soln controls 1.1 ~ 1.3.
Tc controls at 80 ~ 85 DEG C.Crystallization time controls at 20 ~ 90 min, preferably 30 ~ 60 min.
Digestion time controls at 0.5 ~ 24 h, preferably 1 ~ 2 h.
Technical scheme of the present invention is compared with present technology, and tool has the following advantages:
(1) the present invention determines the optimum reaction condition that high-purity iron powder and phosphatase reaction prepare the high-purity Iron phosphate dihydrate of cell-grade, as the initial concentration of phosphoric acid, the reaction mol ratio of iron powder and phosphoric acid, the temperature of iron powder and phosphatase reaction, temperature etc. before oxidation precipitation when the pH value of solution and oxidation precipitation, reactant with high-purity iron powder and phosphoric acid for raw material, both direct anti-biochemical reactions, and the pH value of solution is regulated and controled by the volume of solution, without the need to using ammoniacal liquor, other alkali lye such as sodium hydroxide, thus effectively prevent impurity the moon, positively charged ion or other is inorganic, organic interference, obtain high purity battery level tertiary iron phosphate.
(2) phosphoric acid unnecessary in tertiary iron phosphate only need being gone to precipitate with a small amount of washing, filtrate and washings are only dense or rare phosphoric acid solution, filtrate and washings are merged, namely can be recycled toward wherein adding suitable phosphoric acid, avoid producing trade effluent because using a large amount of deionized water, thus cost is low, belong to eco-friendly friendly process.
(3) technique is simple, easy to operate, and obtain high-purity lamellar nanometer Iron phosphate dihydrate by the pH value and temperature of reaction controlling reaction soln, the tertiary iron phosphate of this pattern is suitable for preparing lithium ion battery anode material lithium iron phosphate.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of tertiary iron phosphate prepared by embodiment 1.
Fig. 2 is the scanning electron microscope diagram of Iron phosphate dihydrate prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, but scope of the present invention is not limited to following embodiment.
Embodiment 1:
115.3 g phosphoric acid (85%) are dissolved in 374.7 g water and are made into the dilute phosphoric acid that mass percentage concentration is 20%, warming-in-water to 40 DEG C, add 500 order reduced iron powder 22.3 g, after stirring reaction 180 min, iron powder dissolves completely, cross the black insoluble solid filtered in solution, obtain the green filtrate clarified.Adding appropriate distilled water regulator solution volume is 400 mL, and the pH of solution is 1.5.Filtrate temperature is increased to 80 DEG C, accompanies by stirring and add 25 mL hydrogen peroxide, stop stirring after reacting 30 min, obtain baby pink tertiary iron phosphate precipitation.Leave standstill after 1 h and filter, with 200 mL water washing filter cake 4 times, filter cake obtains product Iron phosphate dihydrate 71.6 g in 80 DEG C of drying 12 h, and productive rate is 95.8%.
As can be seen from Figure 1 obtained powder is Iron phosphate dihydrate, and exist with metastrengite (kakoxene) crystalline structure, there is not impurity peaks in spectrogram, product purity is high.
As can be seen from Figure 2 particle is plate crystal, and lamellar spacing is 20-40 nm.
Embodiment 2:
Using the filtrate that obtains after filtering tertiary iron phosphate in embodiment 1 and washings mixing as mother liquor, be mixed with toward wherein adding phosphoric acid (85%) dilute phosphoric acid that concentration is 20%, step is below identical with embodiment 1.Finally obtain product Iron phosphate dihydrate 72.2 g, productive rate is 96.6%.
Embodiment 3:
161.4 g phosphoric acid (85%) are dissolved in 387.4 g water and are made into the dilute phosphoric acid that mass percentage concentration is 25%, warming-in-water to 45 DEG C, add 500 order reduced iron powder 22.3 g, after stirring reaction 120 min, iron powder dissolves completely, crosses the black insoluble solid filtered in solution.Adding appropriate distilled water regulator solution volume is 450 mL, and the pH of solution is 0.7.Filtrate temperature is increased to 70 DEG C, accompanies by stirring and add 30 mL hydrogen peroxide, stop stirring after reacting 30 min, obtain baby pink tertiary iron phosphate precipitation.Leave standstill suction filtration after 1 h, with 200 mL water washing filter cake 4 times, filter cake obtains product Iron phosphate dihydrate 65.6 g in 80 DEG C of drying 12 h, and productive rate is 87.8%.
Embodiment 4:
115.3 g phosphoric acid (85%) are dissolved in 276.7 g water and are made into the dilute phosphoric acid that mass percentage concentration is 25%, warming-in-water to 50 DEG C, add 500 order reduced iron powder 22.3 g, after stirring reaction 100 min, iron powder dissolves completely, cross the black insoluble solid filtered in solution, obtain the green filtrate clarified.Adding appropriate distilled water regulator solution volume is 350 mL, and the pH of solution is 1.3.Filtrate temperature is increased to 85 DEG C, accompanies by stirring and add 25 mL hydrogen peroxide, stop stirring after reacting 30 min, obtain baby pink tertiary iron phosphate precipitation.Leave standstill after 1 h and filter, with 200 mL water washing filter cake 4 times, filter cake obtains product Iron phosphate dihydrate 73.7 g in 80 DEG C of drying 12 h, and productive rate is 98.6 %.
Embodiment 5:
115.3 g phosphoric acid (85%) are dissolved in 374.7 g water and are made into the dilute phosphoric acid that mass percentage concentration is 20%, warming-in-water to 40 DEG C, add 300 order electrolytic iron powder 22.3 g, after stirring reaction 300 min, iron powder dissolves completely, cross the black insoluble solid filtered in solution, obtain the green filtrate clarified.Adding appropriate distilled water regulator solution volume is 450 mL, and the pH of solution is 1.8.Filtrate temperature is increased to 90 DEG C, accompanies by stirring and add 30 mL hydrogen peroxide, stop stirring after reacting 30 min, obtain baby pink tertiary iron phosphate precipitation.Leave standstill after 1 h and filter, with 200 mL water washing filter cake 4 times, filter cake obtains product Iron phosphate dihydrate 74.0 g in 80 DEG C of drying 12 h, and productive rate is 99.0%.
Embodiment 6:
144.2 g phosphoric acid (85%) are dissolved in 264.2 g water and are made into the dilute phosphoric acid that mass percentage concentration is 30%, warming-in-water to 50 DEG C, add 500 order reduction electrolytic iron powder 27.9 g, after stirring reaction 80 min, iron powder dissolves completely, cross the black insoluble solid filtered in solution, obtain the green filtrate clarified.Adding appropriate distilled water regulator solution volume is 350 mL, and the pH of solution is 1.1.Filtrate temperature is increased to 80 DEG C, accompanies by stirring and add 40 mL hydrogen peroxide, stop stirring after reacting 30 min, obtain baby pink tertiary iron phosphate precipitation.Leave standstill after 1 h and filter, with 300 mL water washing filter cake 4 times, filter cake obtains product Iron phosphate dihydrate 92.5 g in 80 DEG C of drying 12 h, and productive rate is 99.0%.
The foregoing is only preferred embodiment of the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. prepared a method for battery-grade iron phosphate by iron powder and phosphatase reaction, it is characterized in that iron powder to mix with dilute phosphoric acid, reaction generates Fe (H
2pO
4)
2, then add oxidizing generation tertiary iron phosphate precipitation, after filtration, drying obtains high-purity battery-grade iron phosphate and Iron phosphate dihydrate; Iron phosphate dihydrate is the nano-sheet crystal of metastrengite crystal formation.
2. a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction as claimed in claim 1, is characterized in that it comprises the following steps:
(1) in room temperature or higher than under the condition of room temperature, the iron powder of order number more than 200 orders is dissolved in dilute phosphoric acid, the mass percentage concentration of dilute phosphoric acid controls 15 ~ 45%, and iron powder controls at 1 ︰ 2 ~ 4 with the ratio of the amount of substance of phosphoric acid, until iron powder dissolves completely generate Fe (H
2pO
4)
2, solution becomes blackish green, leaves residuum and insoluble black solid impurity in dissolution process;
(2) by insoluble black solid impurity from Fe (H
2pO
4)
2remove after filtration in solution, obtain the green solution clarified;
(3), at the temperature more than 70 DEG C, crystallization Iron phosphate dihydrate is obtained with the ferrous salt in oxidizing green solution; Before oxidizing reaction occurring, carrying out regulator solution volume by adding water, thus controlling the pH value of reaction soln, pH controls 0.5 ~ 1.8, adds water and is preferably distilled water;
(4) by the ageing under room temperature of crystallization Iron phosphate dihydrate, carry out afterwards filtering, washing and drying, obtain baby pink product and Iron phosphate dihydrate; Iron phosphate dihydrate is the nano-sheet crystal of metastrengite crystal formation.
3. a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction as claimed in claim 2, it is characterized in that, the filtrate produced after ageing and washings recycle: after filtrate and washings being merged, and namely can be used as dilute phosphoric acid recycle toward wherein adding suitable phosphoric acid.
4. a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction as claimed in claim 2, it is characterized in that, the non-limitative example of iron powder comprises the reduced iron powder of weight of iron percentage composition >=98%, the electrolytic iron powder of weight of iron percentage composition >=99%, the spheroidal graphite cast iron powder one of weight of iron percentage composition >=97% or appoints both and three's mixture.
5. a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction as claimed in claim 2, it is characterized in that, the order number of iron powder is 200 ~ 1000 orders; Be preferably 300 ~ 500 orders.
6. a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction as claimed in claim 2, it is characterized in that, the mass percentage concentration of preferred dilute phosphoric acid controls 25 ~ 35%; Preferred iron powder and the ratio of the amount of substance of phosphoric acid control at 1 ︰ 2.5 ~ 3; Preferred iron powder is dissolved in temperature of reaction in dilute phosphoric acid and controls at 20 ~ 60 DEG C, and further preferable reaction temperature controls at 40 ~ 50 DEG C.
7. a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction as claimed in claim 2, is characterized in that, before oxidizing reaction occurs, the pH of reaction soln controls 1.1 ~ 1.3.
8. a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction as claimed in claim 2, is characterized in that, the non-limitative example of oxygenant comprises hydrogen peroxide, ozone or both are used in combination.
9. a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction as claimed in claim 2, it is characterized in that, Tc controls at 80 ~ 85 DEG C; Preferred crystallization time controls at 20 ~ 90 min, and preferably crystallization time controls at 30 ~ 60 min further.
10. a kind of method being prepared battery-grade iron phosphate by iron powder and phosphatase reaction as claimed in claim 2, it is characterized in that, digestion time controls at 0.5 ~ 24 h, preferably 1 ~ 2 h.
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| CN116534824A (en) * | 2023-06-01 | 2023-08-04 | 云南云天化股份有限公司 | Method for preparing ferric phosphate by continuous oxidation process |
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