CN102051629A - Method for preparing FexPO4 by electrolyzing ferrophosphorus - Google Patents
Method for preparing FexPO4 by electrolyzing ferrophosphorus Download PDFInfo
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- CN102051629A CN102051629A CN 201010546421 CN201010546421A CN102051629A CN 102051629 A CN102051629 A CN 102051629A CN 201010546421 CN201010546421 CN 201010546421 CN 201010546421 A CN201010546421 A CN 201010546421A CN 102051629 A CN102051629 A CN 102051629A
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- ferrophosphorus
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Abstract
The invention relates to a method for preparing FexPO4 by electrolyzing ferrophosphorus, which comprises the following steps: by using ferrophosphorus as the anode and providing an oxygen source by using oxygen in water as the product, electrolyzing to obtain a FexPO4 solution, wherein only ferrophosphorus and water are consumed in the reaction process; adding basic oxides to regulate the pH value of the solution so as to settle out FexPO4; and granulating, filtering and washing to obtain the finished FexPO4 product. In the method, cheap ferrophosphorus is converted into high-value FexPO4 by using the electrolytic reaction process; the source of ferrophosphorus is not limited; the influence of impurity elements on the product can be eliminated; the product can be granulated into controlled shape and particle size; the byproduct H2 can be recycled; the treated filtrate can be used cyclically; the obtained finished FexPO4 product has the advantages of high purity, small particle size, easily controlled shape, and low power consumption; the reaction process has low requirements for equipment and is easy to operate; and the preparation method has the advantages of simple technique, high resource utilization rate, low cost, low investment, good benefit, high cleanness and environmental protection, can be easily industrialized, and is suitable for high-value comprehensive utilization of byproducts in chemical industry and large-scale industrial low-cost clean production of high-end phosphates.
Description
Technical field
The present invention relates to a kind of by ferrophosphorus electrolytic preparation Fe
xPO
4Method, utilize reaction process to eliminate in the raw material impurity to the influence of product, degree of purity of production height, fine size, pattern are easy to control, technology is simple, can be applicable to the high value comprehensive utilization of chemical industry solid waste and the low-cost cleaner production of high-end phosphate material.
Background technology
Fe
xPO
4Be a kind of phosphoric acid salt of iron, be widely used in fields such as energy and material, catalyzer, pottery, foodstuff additive.In field of energy source materials, Fe
xPO
4(its chemical property is subjected to the crystalline form of material and preparation method's influence bigger, wherein amorphous FePO itself can be used as electrode materials
4Operating voltage be 3V), also can be used as the preparation LiFePO
4, LiFeP
2O
7And Li
3Fe
2(PO
4)
3Raw material Deng electrode materials.Because Fe and P are at Fe
xPO
4In disperseed more evenly, only need Li
+Diffusion enters just to obtain containing the lithium electrode material, from theoretical analysis and practice result, by Fe
xPO
4Electrode materials is easier carries out in preparation, therefore a large amount of at present Fe that adopt
xPO
4Simultaneously prepare LiFePO as source of iron and phosphorus source
4And Li
3Fe
2(PO
4)
3Deng electrode materials.Prepare FePO at present
4Usually be raw material with iron powder or molysite and phosphoric acid or phosphoric acid salt, stirring reaction under solution state, after 90～100 ℃ of oven dry, cure and obtain tertiary iron phosphate at 600～800 ℃, produce a large amount of waste liquids in the reaction process, there are problems such as reaction process is difficult to control, raw material is single and cost is high, equipment corrosion is serious, the liquid waste disposal difficulty is big, cost height, cause present FePO
4Market value higher, reach 2～30,000/ton, thereby the cost for preparing LiFePO 4 by tertiary iron phosphate can not fallen.
Ferrophosphorus is the alloy that phosphorus and iron form, metalluster slightly, and proportion is bigger, aboundresources, wide material sources can be mineral or its smelting product, it also can be the by product during phosphorous chemical industry such as yellow phosphorus or fused(calcium magnesium)phosphate and silicate chemical industry etc. are produced, also can make by oneself, output is bigger, and only electric furnace process is produced in the phosphorus technology, produce 80～150 kilograms of 1 ton of yellow phosphorus by-product ferrophosphorus, wherein, w (P)=18%-26%, w (Fe)=70%.The ferrophosphorus aboundresources of China, Application Areas is very limited, and market value is lower, and most of cheapness exports or is purchased with crude product by commerce and trade department.
In order to expand the Application Areas of ferrophosphorus, improve the added value of ferrophosphorus, we have carried out a large amount of work at ferrophosphorus, taken the lead in proposing utilizing the abundant inexpensive ferrophosphorus in source to prepare new approaches [the Chinese patent ZL200810045243.1 of electrode materials, CN101602500A, CN101659408A, 200910263487.1,20091063486.7,200910263552.0,200910263553.5,201010126920.X.] and prepare the special implementing process [Chinese patent CN101659406A] of tertiary iron phosphate by ferrophosphorus.In these methods, prepare electrode materials by ferrophosphorus and reach special emphasis and the processing method difference for preparing tertiary iron phosphate by ferrophosphorus, adopt different novel techniques to produce different effects.Prepare in the special implementing process [Chinese patent CN101659406A] of tertiary iron phosphate at our former cause ferrophosphorus, relying on ferrophosphorus high temperature oxidation in dry oxygen-containing atmosphere is Fe
2O
3And P
2O
5After again secondary response reduce impurity element in the ferrophosphorus to the influence of product, directly prepare the controlled tertiary iron phosphate of pattern by ferrophosphorus is carried out the electrolysis removal of impurities at normal temperature, obviously different with the application's technology and technology.In addition, dopant species in the ferrophosphorus that different regions different process obtains and content difference cause to be difficult to ferrophosphorus is purified comprehensively.Yet these impurity can exert an influence to the performance of product, need carry out certain purification processes to it.In addition, when directly preparing tertiary iron phosphate, need in the dry oxidizing atmosphere of comparatively high temps, finish by ferrophosphorus, reaction process complexity and cost height, than higher, the granularity of product is difficult to control simultaneously, is subjected to the particle size influences of ferrophosphorus raw material bigger to the requirement of equipment.
In order to overcome present Fe
xPO
4The deficiency of production technique, solution prepares Fe by ferrophosphorus
xPO
4The time dopant species and content are uncertain in high temperature drying oxidizing atmosphere, the ferrophosphorus raw material causes being difficult to purify impurity element and Fe comprehensively
xPO
4The unmanageable technical barrier of product granularity and pattern is simplified preparation technology, cuts down the consumption of energy, and reduces the discharging of refuse, the present invention proposes a kind of and the diverse novel process method of foregoing invention: with ferrophosphorus electrolytic preparation Fe in the aqueous solution
xPO
4, applying 1～20V voltage, current density is 5～1500A m
-2, electrolysis obtains Fe
xPO
4Solution adds basic oxide, and the pH value of regulator solution is 1～8, with Fe
xPO
4Be precipitated out, after filtration, washing obtains Fe
xPO
4Finished product.By using anode and control electrolytic process parameter, the impurities in raw materials element is removed, make the purity of this product higher and granularity is controlled with pattern, can directly use, also can be further used as the raw material of production other materials.The present invention innovates from the source, a kind of novel technical route of creationary proposition by ferrophosphorus room temperature electrolytic preparation tertiary iron phosphate, reaction conditions is simple, can and adopt anode that ferrophosphorus is purified by the control electrolytic process parameter simultaneously, the raw material ferrophosphorus of use be subjected to impurity to limit wide material sources, only consume ferrophosphorus and water in the reaction process, do not have the consumption of other materials, cost is lower, can be to Fe in the aqueous solution
xPO
4Carry out granulation and handle, the hydrogen of a large amount of by-products can be used as clean energy and is recycled, and filtrate can be used as fertilizer after treatment or circular electrolyte is recycled, and the precious metal in the anode also can utilize after the enrichment.Fe by the present invention's preparation
xPO
4The degree of purity of production height, granularity is little, pattern is easy to control, and raw materials cost is low, and current consumption is low, and is low for equipment requirements, pollutes fewly, and reaction process is short, and preparation method's technology is simple, and clean environment firendly reacts easy to operate, profitable.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art in order to address the above problem, simplification prepares Fe by ferrophosphorus
xPO
4The reaction process flow process, creationary proposition is a kind of by ferrophosphorus electrolytic preparation Fe in the aqueous solution
xPO
4Brand-new processing method, utilize the oxygen in the water to provide oxygen source for product, can carry out granulation to product and handle, the hydrogen of by-product can be used as clean energy and is recycled, and filtrate can recycle after treatment, and current consumption is low, energy-saving and emission-reduction, low for equipment requirements.
Basic design of the present invention is: the present invention utilizes that the oxygen of water makes the P of ferrophosphorus be oxidized to PO in the electrolytic solution
4 3-, PO
4 3-Again with ferrophosphorus in the iron effect form Fe
xPO
4In reaction system, realize the redox reaction material balance of raw material and electrolytic solution, and can utilize the redox potential of different elements that ferrophosphorus is purified, also can carry out the granulation processing to the aqueous solution of product and obtain the product of different-grain diameter and pattern, thereby make the Fe of preparation
xPO
4Purity height, pattern and controllable granularity.
Of the present inventionly prepare the method for tertiary iron phosphate by ferrophosphorus, concrete processing step is as follows;
1) with the ferrophosphorus be anode, inert material is a negative electrode, and the aqueous solution is electrolytic solution, applies 1～20V voltage, and current density is 5～1500Am
-2, electrolysis obtains Fe
xPO
4Solution;
2) adding basic oxide, to adjust the pH value of above-mentioned solution be 1～8, with Fe
xPO
4Be precipitated out;
3) after filtration, the washing, obtain Fe
xPO
4Finished product.
The total reaction equation of the present invention is as follows:
Fe
xP+4H
2O→Fe
xPO
4+4H
2↑
Among the present invention, the basic oxide of described interpolation can be for the oxyhydroxide or the carbonate of lithium, sodium, potassium, rubidium, ammonium, as LiOH, NaOH, KOH, RbOH, Li
2CO
3, NH
3H
2O, (NH
4)
2CO
3Deng.
Among the present invention, described Fe
xPO
4In, 0＜x=2 especially refers to tertiary iron phosphate, ferrous phosphate.
Among the present invention, described ferrophosphorus anode can be placed in the anode, filters out the impurity in the anode, improves Fe
xPO
4Finished product purity, the precious metal in the anode also can utilize after the enrichment simultaneously.
Among the present invention, can add phosphoric acid, H in the described aqueous electrolyte
2SO
4, HNO
3, CH
3COOH and an alkali metal salt thereof.
Among the present invention, add NH
3H
2O or (NH
4)
2CO
3Regulate Fe
xPO
4The pH value of solution filters out Fe
xPO
4After, rest solution can be made chemical fertilizer.
Among the present invention, add LiOHH
2O or Li
2CO
3Regulate Fe
xPO
4The pH value of solution can co-precipitation go out iron lithium phosphate or LiFePO 4.
Among the present invention, described negative electrode inert material can be graphite, platinum, lead, titanium and alloy thereof.
Among the present invention, can carry out specific aim to ferrophosphorus by electrolysis voltage or current density and purify.
Among the present invention, can control Fe by processing condition
xPO
4The pattern of product, degree of crystallinity and size and distribution etc. also can be carried out ball milling or aftertreatments such as comminution by gas stream, modification to product as required.
The present invention compared with prior art the invention solves by ferrophosphorus and prepares Fe
xPO
4The time the keeping of high temperature drying oxidizing atmosphere, ferrophosphorus raw material impurity element to the influence and the Fe of product
xPO
4The unmanageable series technique difficult problem of product granularity and pattern, overcome the problem of forming the proportioning raw materials difficulty that diversity causes by ferrophosphorus, the consumption of big energy and equipment is perishable and the slow-footed deficiency of gas-solid reaction when having eliminated the ferrophosphorus oxidation, the novel preparation method that creationary proposition " utilizes the oxygen in the water oxygen source to be provided for the P in the ferrophosphorus; to realize the material balance of redox reaction in ferrophosphorus and the water system ", do not need to replenish in addition other oxygen sources, utilize reaction process can reduce impurity element influence and product is carried out granulation, have the following advantages and the high-lighting effect: the reaction process uniqueness, by reaction is designed, make Fe
xPO
4Oxygen in the product comes from inexpensive water fully, realizes that ferrophosphorus single step reaction in water just can easier obtain Fe
xPO
4Product has only the consumption of ferrophosphorus and water in the reaction process, do not have the consumption of other materials, does not require forming as the ferrophosphorus of raw material, and it is very extensive to originate, and raw material is cheap and easy to get, and cost is low; Ferrophosphorus is applied electric current as anode in the aqueous solution, just can electrolysis go out Fe
xPO
4, after the phosphorus in the ferrophosphorus and iron adjusted in proportion, phosphorus and iron in the ferrophosphorus are utilized cmpletely, there are not other by products to produce, realize the environmental protection cleaner production; Can eliminate in the raw material impurity element to the influence of product, ferrophosphorus effectively be purified by control electrolysis voltage and current density; Can effectively control Fe
xPO
4The pattern of product and size-grade distribution are by to Fe
xPO
4Solution carries out measures such as granulation, crystallization can effectively control Fe
xPO
4The pattern of product and size-grade distribution can easier obtain receiving the sphere material of microscale; By-product clean energy hydrogen, a large amount of hydrogen that produce can easier be recycled, and environment is safe from harm; Have only the consumption of ferrophosphorus and water in the reaction process, raw materials cost is low, and filtrate after treatment can recycle, and environment is safe from harm; Reaction raw materials is single, does not need that raw material is carried out mixing and handles, and technology is simple; Use anode will utilize behind the concentration of precious metal in the ferrophosphorus; The current consumption of reaction is few, energy-saving and emission-reduction, and lower to the requirement of equipment, technical process is simple, and is easy to operate, low production cost, three-waste free pollution, clean environment firendly, the resource utilization height, less investment, profitable.
Description of drawings
Fig. 1 is by ferrophosphorus Fe
1.5P, H
3PO
4FePO for feedstock production
4XRD figure.
Fig. 2 is by synthetic FePO
4With LiOHH
2O is the LiFePO of feedstock production
4XRD figure.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing; described content only is the basic explanation of the present invention under conceiving; but the present invention is not limited to following example, and any equivalent transformation according to technical scheme of the present invention is done all belongs to protection scope of the present invention.
Embodiment 1
Adopt electrolytic process to prepare tertiary iron phosphate by ferrophosphorus, FeP prepares FePO with ferrophosphorus
4, ferrophosphorus and graphite are formed electrolyzer, ferrophosphorus is done anode, be placed in the anode, graphite is done negative electrode, and tap water is done electrolytic solution, the phosphoric acid of interpolation 1% increases electroconductibility, separate at electrifying DC power supply, voltage is 5～7V, and electric current is 1.5～2A, electrolysis time is 50～60h, regulate pH=5～6 with adding ammoniacal liquor in the solution after the electrolysis,, obtain the tertiary iron phosphate finished product through filtration, washing, oven dry.
In this reaction, add ammoniacal liquor and regulate the pH value, filtering the back rest solution is ammonium phosphate, can use as chemical fertilizer, has realized the environmental protection cleaner production.
Embodiment 2
Adopt electrolytic process by ferrophosphorus Fe
2P prepares tertiary iron phosphate, is that source of iron and part phosphorus source prepare FePO with the ferrophosphorus
4, ferrophosphorus and graphite are formed electrolyzer, ferrophosphorus is done anode, graphite is done negative electrode, and the aqueous solution is done electrolytic solution, is additional phosphorus source with phosphoric acid, also improved simultaneously the electroconductibility of the aqueous solution, separate at electrifying DC power supply, voltage is 4～6V, and electric current is 1.5～2A, electrolysis time is 30～40h, regulate pH=4～5 with adding volatile salt in the solution after the electrolysis,, obtain the tertiary iron phosphate finished product through filtration, washing, oven dry.
In this reaction, add volatile salt and regulate pH, filtering the back rest solution is ammonium phosphate, can realize the environmental protection cleaner production as chemical fertilizer.
Embodiment 3
Adopt electrolytic process by ferrophosphorus Fe
1.5P prepares ferrous phosphate, is that source of iron and part phosphorus source prepare Fe with the ferrophosphorus
3(PO
4)
2, ferrophosphorus and graphite are formed electrolyzer, ferrophosphorus is done anode, be placed in the anode, graphite is done negative electrode, and the aqueous solution is done electrolytic solution, for replenishing the phosphorus source, also improved the electroconductibility of the aqueous solution with ammonium phosphate simultaneously, separated at electrifying DC power supply, voltage is 5～7V, electric current is 1.8～2A, and electrolysis time is 40～45h, transfers pH=6～7 with adding bicarbonate of ammonia in the solution after the electrolysis, through filtering, wash, drying, obtain the ferrous phosphate finished product.
In this reaction, add ammoniacal liquor and regulate pH, filtering back rest solution (ammonium phosphate) can be as chemical fertilizer.Realized the environmental protection cleaner production.
Embodiment 4
Adopting electrolytic process to prepare tertiary iron phosphate by ferrophosphorus FeP, is that source of iron and part phosphorus source prepare FePO with the ferrophosphorus
4Ferrophosphorus and graphite are formed electrolyzer, and ferrophosphorus is done anode, is placed in the anode, graphite is done negative electrode, the aqueous solution is done electrolytic solution, in order to increase electroconductibility, in the aqueous solution, add Trilithium phosphate, separating voltage at electrifying DC power supply is 5～7V, and electric current is 1.5～2A, and electrolysis time is 35～40h, transfer pH=4～5 with adding lithium hydroxide in the solution after the electrolysis, through filtering, washing, oven dry obtains tertiary iron phosphate, 600～650 ℃ of roastings, crystalline structure after roasting as shown in Figure 1, the material of co-precipitation generates the LiFePO 4 energy and material 650～700 ℃ of roastings after roasting, realize cleaner production.
Embodiment 5
Adopt electrolytic process by ferrophosphorus Fe
1.5P prepares ferrous phosphate, is that source of iron and part phosphorus source prepare Fe with the ferrophosphorus
3(PO
4)
2Ferrophosphorus and graphite are formed electrolyzer, ferrophosphorus is done anode, and graphite is done negative electrode, and the aqueous solution is done electrolytic solution, in order to increase electroconductibility, in the aqueous solution, add Trilithium phosphate, separate at electrifying DC power supply, separating voltage at electrifying DC power supply is 5～7V, electric current is 1.5～2A, and electrolysis time is 45～50h, transfers pH=3～4 with adding Quilonum Retard in the solution after the electrolysis, through filtering, wash, drying, obtain ferrous phosphate, form co-precipitation, the material of co-precipitation is 650～700 ℃ of roastings, generate LiFePO 4 after roasting, the crystalline structure after roasting as shown in Figure 2.Filtrate can recycle, realizes cleaner production.
Embodiment 6
Adopt electrolytic process by ferrophosphorus Fe
1.5P prepares ferrous phosphate, is that source of iron and part phosphorus source prepare Fe with the ferrophosphorus
3(PO
4)
2, ferrophosphorus and graphite are formed electrolyzer, ferrophosphorus is done anode, be placed in the anode, graphite is done negative electrode, and sodium phosphate is done electrolytic solution, separate at electrifying DC power supply, separating voltage at electrifying DC power supply is 4～6V, and electric current is 1.5～2A, and electrolysis time is 40～50h, transfer pH=3～4 with adding sodium hydroxide in the solution after the electrolysis, through filtering, washing, oven dry obtains the ferrous phosphate finished product.
Embodiment 7
Adopting electrolytic process to prepare tertiary iron phosphate by ferrophosphorus FeP, is that source of iron and part phosphorus source prepare FePO with the ferrophosphorus
4, ferrophosphorus and graphite are formed electrolyzer, ferrophosphorus is done anode, be placed in the anode, graphite is done negative electrode, and the aqueous solution is done electrolytic solution, in order to increase electroconductibility, in the aqueous solution, add potassiumphosphate, separate at electrifying DC power supply, separating voltage at electrifying DC power supply is 5～7V, and electric current is 1.5～1.8A, electrolysis time is 45～50h, transfer pH=4～5 with adding potassium hydroxide in the solution after the electrolysis,, obtain the tertiary iron phosphate finished product through filtration, washing, oven dry.
Embodiment 8
Adopting electrolytic process to prepare tertiary iron phosphate by ferrophosphorus FeP, is that source of iron and part phosphorus source prepare FePO with the ferrophosphorus
4, ferrophosphorus and graphite are formed electrolyzer, ferrophosphorus is done anode, graphite is done negative electrode, and the aqueous solution is done electrolytic solution, in order to increase electroconductibility, in the aqueous solution, add sodium phosphate, separate at electrifying DC power supply, separating voltage at electrifying DC power supply is 5～7V, and electric current is 1.5～2A, and electrolysis time is 40～50h, with the solution after the electrolysis, add yellow soda ash and transfer pH=5～6,, obtain the tertiary iron phosphate finished product through filtration, washing, oven dry.
Claims (8)
1. the electrolysis ferrophosphorus prepares Fe
xPO
4Method, be raw material with the ferrophosphorus, x is that different chemical is formed determined coefficient, it is characterized in that processing step is as follows:
1) with the ferrophosphorus be anode, inert material is a negative electrode, and the aqueous solution is electrolytic solution, applies 1～20V voltage, and current density is 5～1500Am
-2, electrolysis obtains Fe
xPO
4Solution;
2) adding basic oxide, to adjust the pH value of above-mentioned solution be 1～8, with Fe
xPO
4Be precipitated out;
3) after filtration, the washing, obtain Fe
xPO
4Finished product.
2. according to the description of claim 1, it is characterized in that: the basic oxide of interpolation can be for the oxyhydroxide or the carbonate of lithium, sodium, potassium, rubidium, ammonium, as LiOH, NaOH, KOH, RbOH, Li
2CO
3, NH
3H
2O, (NH
4)
2CO
3
3. according to the description of claim 1, it is characterized in that: described Fe
xPO
4In, 0＜x=2 especially refers to tertiary iron phosphate, ferrous phosphate.
4. according to the description of claim 1, it is characterized in that: according to the description of claim 1, ferrophosphorus is done anode, can be placed in the anode, filters out the impurity in the anode, improves Fe
xPO
4Finished product purity.
5. describe according to claim 1, it is characterized in that: as adding phosphoric acid, H in the aqueous solution of electrolytic solution
2SO
4, HNO
3, CH
3COOH and an alkali metal salt thereof.
6. according to the description of claim 1 and claim 2, it is characterized in that: add NH
3H
2O or (NH
4)
2CO
3Regulate Fe
xPO
4The pH value of solution filters out Fe
xPO
4After, rest solution can be made chemical fertilizer.
7. according to the description of claim 1, claim 2 and claim 3, it is characterized in that: add LiOH or Li
2CO
3Regulate Fe
xPO
4The pH value of solution can co-precipitation go out iron lithium phosphate or LiFePO 4.
8. according to the description of claim 1, it is characterized in that: the inert material as negative electrode can be graphite, platinum, lead, titanium and alloy thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010546421 CN102051629B (en) | 2010-11-17 | 2010-11-17 | Method for preparing FexPO4 by electrolyzing ferrophosphorus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010546421 CN102051629B (en) | 2010-11-17 | 2010-11-17 | Method for preparing FexPO4 by electrolyzing ferrophosphorus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102051629A true CN102051629A (en) | 2011-05-11 |
| CN102051629B CN102051629B (en) | 2013-01-02 |
Family
ID=43956417
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010546421 Expired - Fee Related CN102051629B (en) | 2010-11-17 | 2010-11-17 | Method for preparing FexPO4 by electrolyzing ferrophosphorus |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086341A (en) * | 2013-02-04 | 2013-05-08 | 瓮福（集团）有限责任公司 | Method for preparing battery-grade iron phosphate by using ferrophosphorus |
| CN103556169A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Dandelion-shaped iron phosphate microspheres and preparation method thereof through electrochemical anode oxidation |
| CN106006597A (en) * | 2016-05-24 | 2016-10-12 | 四川大学 | Method for preparing FexPO4-containing substances from ferrophosphorus at low temperature |
| CN110048120A (en) * | 2019-04-23 | 2019-07-23 | 王柯娜 | A kind of preparation method of nanometer of ferrous acid lithium |
| CN111411366A (en) * | 2020-04-26 | 2020-07-14 | 华中科技大学 | Method for recovering metal ions in lithium iron phosphate waste through solid-phase electrolysis |
| CN111663147A (en) * | 2020-05-11 | 2020-09-15 | 湖南雅城新材料有限公司 | Process for preparing iron phosphate by electrolytic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109023463A (en) * | 2018-06-29 | 2018-12-18 | 洛阳师范学院 | A kind of Ni2P2O7The preparation method of film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2133289A (en) * | 1936-10-15 | 1938-10-18 | Lewis H D Fraser | Anodic oxidation of ferrophosphorus |
| US2173103A (en) * | 1936-10-15 | 1939-09-19 | Lewis H D Fraser | Anodic oxidation of ferrophosphorus |
-
2010
- 2010-11-17 CN CN 201010546421 patent/CN102051629B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2133289A (en) * | 1936-10-15 | 1938-10-18 | Lewis H D Fraser | Anodic oxidation of ferrophosphorus |
| US2173103A (en) * | 1936-10-15 | 1939-09-19 | Lewis H D Fraser | Anodic oxidation of ferrophosphorus |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086341A (en) * | 2013-02-04 | 2013-05-08 | 瓮福（集团）有限责任公司 | Method for preparing battery-grade iron phosphate by using ferrophosphorus |
| CN103556169A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Dandelion-shaped iron phosphate microspheres and preparation method thereof through electrochemical anode oxidation |
| CN103556169B (en) * | 2013-11-15 | 2016-01-20 | 哈尔滨工业大学 | A kind of taraxacum shape tertiary iron phosphate micron ball and method for preparing electrochemical anodic oxidation thereof |
| CN106006597A (en) * | 2016-05-24 | 2016-10-12 | 四川大学 | Method for preparing FexPO4-containing substances from ferrophosphorus at low temperature |
| WO2017201911A1 (en) * | 2016-05-24 | 2017-11-30 | 四川大学 | Method for low temperature manufacturing of fexpo4-containing material using ferrophosphorus |
| CN106006597B (en) * | 2016-05-24 | 2019-04-16 | 四川大学 | One kind containing Fe by ferrophosphorus low temperature preparationxPO4The method of substance |
| CN110048120A (en) * | 2019-04-23 | 2019-07-23 | 王柯娜 | A kind of preparation method of nanometer of ferrous acid lithium |
| CN111411366A (en) * | 2020-04-26 | 2020-07-14 | 华中科技大学 | Method for recovering metal ions in lithium iron phosphate waste through solid-phase electrolysis |
| CN111663147A (en) * | 2020-05-11 | 2020-09-15 | 湖南雅城新材料有限公司 | Process for preparing iron phosphate by electrolytic method |
| CN111663147B (en) * | 2020-05-11 | 2021-09-03 | 湖南雅城新材料有限公司 | Process for preparing iron phosphate by electrolytic method |
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