CN107032316A - A kind of preparation method of ferric phosphate - Google Patents
A kind of preparation method of ferric phosphate Download PDFInfo
- Publication number
- CN107032316A CN107032316A CN201710438654.6A CN201710438654A CN107032316A CN 107032316 A CN107032316 A CN 107032316A CN 201710438654 A CN201710438654 A CN 201710438654A CN 107032316 A CN107032316 A CN 107032316A
- Authority
- CN
- China
- Prior art keywords
- iron
- ferric phosphate
- phosphoric acid
- preparation
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to technical field of energy material, specifically disclose a kind of preparation method of ferric phosphate, the oxide of a small amount of iron is added to obtain the fabulous phosphoric acid iron product of epigranular tap density as raw material and phosphoric acid generation ferric phosphate, then by washing, drying using purer iron.The processing of the salt of a large amount of by-products when the method that the present invention prepares ferric phosphate avoids phosphate with molysite production ferric phosphate；The performance of ferric phosphate is controlled by high-pressure oxidation process, the performances such as tap density are effectively improved；By by phosphoric acid rectification and purification reuse, effectively reducing material loss, the phosphorus content for reducing sewage reduces sewage disposal difficulty, reaches the purpose of green production.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, and in particular to a kind of preparation method of ferric phosphate.
Background technology
Ferric phosphate is also known as high ferric phosphate, and English name is iron (iii) phosphate tetrahydrate, and No. CAS is
10045-86-0。
Lithium ion battery is the green high-capacity battery of a new generation, with voltage is high, energy density is big, good cycle, from
The many merits such as small, memory-less effect, the operating temperature range of discharging be wide, are widely used in mobile phone, notebook computer, number
Camera, video camera, electronic instrument etc., also have in fields such as UPS, electric tool, electric bicycle, electric automobile, energy-storage batteries
There is the application prospect of light.In recent years, the yield of lithium ion battery is skyrocketed through, and application field constantly expands, it has also become two
The eleventh century new high-tech product significant to national economy and people's lives.
At present, lithium ion battery has reached its maturity in the compact battery field of portable type electronic product, and application is just
Progressively to middle Large Copacity, in high-power power type and accumulation energy type field of batteries expand.Positive electrode is the weight of lithium ion battery
Part is wanted, its performance largely determines the combination property of battery.Positive electrode is studied and performance improvement is lithium
One of core of ion battery development.
Ferric phosphate is as the raw material for the LiFePO4 for making lithium battery, and with the utilization of new energy, its demand is increasing,
The production technology of current ferric phosphate is generally that phosphate produces ferric phosphate with molysite, and rarer phosphoric acid directly produces ferric phosphate with iron
Technique, phosphate is above phosphoric acid with molysite production its production time of ferric phosphate and energy consumption and iron directly produces ferric phosphate, and
There are other salt as by-product, the sale processing of a large amount of by-product salt is more difficult.Because the impurity of molysite is higher, for ferric phosphate
Production purification has bigger difficulty, and using the technique of molysite, the technological requirement to purification is higher, and iron powder and its oxide purity are general
All over higher, beneficial to the constraint carried out to its impurity, it can guarantee that its impurity content is extremely low for production ferric phosphate.It is such as sub- using sulfuric acid
Iron is raw material, it is necessary to consider the content of the wherein metal ion such as titanium, in addition it is also necessary to the problem of considering processing sulfate radical, but uses iron
If powder, common metal ion concentration highest is manganese, although claims, but can be selected not to this in ferric phosphate national standard
The extremely low iron powder of manganese content is as raw material, i.e., the iron powder of only hundreds of ppm manganese contents is raw material, you can by the metal ion of product
Content is controlled within 100ppm.
The ferric phosphate produced using iron and its oxi as source of iron, the ferric phosphate of contrast molysite production has its advantage, but
Than the phosphoric acid iron product of molysite production, its crystal formation is slightly worse, and granularity is larger, is that a comparison is urgent for ferric phosphate production
The problem of needing to solve.
The content of the invention
The present invention is intended to provide a kind of preparation method of ferric phosphate, uses purer iron to add the oxide conduct of a small amount of iron
Raw material and phosphoric acid produce ferric phosphate, it is to avoid the processing of the salt of a large amount of by-products when phosphate with molysite produces ferric phosphate, have simultaneously
Efficiency makes it have splendid crystal formation and relatively low granularity, and controls its metal ion content within 100ppm, reaches green
The purpose of production.
In order to solve the above technical problems, a kind of preparation method of ferric phosphate of the invention, preparation method is as follows：
It is prepared by S1, ferrous phosphate：By in source of iron and phosphoric acid and phosphoric acid mother liquor input reactor, add distilled water configuration and contain admittedly
5%-15%, heating, stirring, reacts 0.5-2h at a temperature of 60-100 DEG C；Filtered again, filtrate is ferrous phosphate mother liquor；
S2, ferric phosphate preparation：By ferrous phosphate and hydrogen peroxide mol ratio 1 in autoclave pressure:0.5-2 ratio is to phosphorus
30% hydrogenperoxide steam generator is put into sour ferrous iron mother liquor, 40-60 DEG C of progress synthesis under normal pressure is warming up to, is warming up to 90-120 DEG C of progress
Reaction under high pressure, then filtered, filter residue is ferric phosphate crude product, and filtrate is phosphoric acid mother liquor after rectifying column rectification and purification, is returned
With to ferrous phosphate preparatory phase；
S3, washing：Ferric phosphate crude product is configured using distilled water, solution contains 5%-50% admittedly, is warming up to 60-80 DEG C of stirring
Washing, repeated washing after filtering；
S4, drying：By the phosphoric acid iron product after the completion of washing in drying 8-12h in 80-100 DEG C of drying box, that is, obtain
Phosphoric acid iron product.
Further, source of iron described in S1 is one kind or many in iron powder, di-iron trioxide, ferroso-ferric oxide or pure iron
Kind.
Specifically, the source of iron and phosphorylated ligand ratio are 1:1.01-1.03.
Further, synthesis under normal pressure time described in S2 is 0.5-1h, and the reaction under high pressure time is 1-2h.
Further, the agitator treating time is 15-30mi n in S3, and pH value is close to 7 after repeated washing.
The beneficial effects of the invention are as follows：
1) directly use the oxide of iron powder, pure iron and iron as raw material, the technique that it prepares ferrous phosphate is relatively simple,
Effectively solve phosphate and molysite and enter line replacement reaction and be made to need after ferrous phosphate to asking that the salt of reaction by-product is handled
Topic, substantial amounts of by-product salt is worth relatively low, sales difficulty, also add the energy consumption and artificial, equipment cost of production；
2) performance of ferric phosphate is controlled by high-pressure oxidation process, the performances such as tap density are effectively improved；
3) by by phosphoric acid rectification and purification reuse, effectively reducing material loss, the phosphorus content for reducing sewage is reduced
Sewage disposal difficulty.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained on the premise of creative work is not made, belongs to what the present invention was protected
Scope.
In the specific embodiment of the present invention, a kind of preparation method of ferric phosphate is disclosed, preparation method is as follows：
S1, by mol ratio 1:1.01 0.5mol iron powders are put into reactor with 0.505mol phosphoric acid with phosphoric acid mother liquor, plus
Enter distilled water to be assigned to admittedly containing 5%, be progressively warming up to 96 DEG C of reaction 0.5h, filtering；
S2, filtrate added into reactor, add the hydrogen peroxide of 0.25mol 30% by iron powder mol ratio, be warming up to 60 DEG C of guarantors
Warm 0.5h, is warming up to 100 DEG C, is incubated 2h, and filtering obtains ferric phosphate crude product；
S3, by ferric phosphate crude product add reactor, add distilled water configuration admittedly contain 5%, be warming up to 80 DEG C of agitator treatings
15min, filtering, repeated washing 3 times, PH is close to 7, and washing is completed；
S4, phosphoric acid iron product dried into 10h in 80 DEG C of baking ovens, obtain phosphoric acid iron product.
Product yield is calculated with source of iron and reaches 99%, granularity reaches that 3.2um meets HG/T4701-2014《Battery phosphoric acid
Iron》Industry code requirements, tap density reaches 0.80g/cm3, meets HG/T4701-2014《Battery ferric phosphate》Professional standard
It is required that.
In another specific embodiment of the present invention, a kind of preparation method of ferric phosphate is disclosed, preparation method is as follows：
S1, by mol ratio 1:1.03 0.6mol pure iron is put into reactor with 0.609mol phosphoric acid and phosphoric acid mother liquor, plus
Enter distilled water to be assigned to admittedly containing 15%, be progressively warming up to 90 DEG C of reaction 1h, filtering；
S2, filtrate added into reactor, by pure iron mol ratio 1:1 adds 0.6mol30% hydrogen peroxide, is warming up to 60 DEG C
1h is incubated, 120 DEG C are warming up to, 1h is incubated, filtering obtains ferric phosphate crude product；
S3, by ferric phosphate crude product add reactor, add distilled water configuration admittedly contain 30%, be warming up to 80 DEG C of agitator treatings
15min, filtering；Repeated washing 3 times, PH is close to 7, and washing is completed.
S4,8h will be dried in phosphoric acid iron product and 100 DEG C of baking ovens；Phosphoric acid iron product can be obtained.
Product yield is calculated with source of iron and reaches 99%, granularity reaches that 4.0um meets HG/T4701-2014《Battery phosphoric acid
Iron》Industry code requirements, tap density reaches 0.78g/cm3, meets HG/T4701-2014《Battery ferric phosphate》Professional standard
It is required that.
In another specific embodiment of the present invention, a kind of preparation method of ferric phosphate is disclosed, preparation method is as follows：
S1, by mol ratio 1:1.02 0.4mol di-iron trioxides and 0.408mol phosphoric acid and phosphoric acid mother liquor input reactor
In, add distilled water and be assigned to admittedly containing 10%, be progressively warming up to 92 DEG C of reaction 0.5h, filtering；
S2, filtrate added into reactor, by source of iron mol ratio 1:1.5 add 0.6mol30% hydrogen peroxide, are warming up to 50
DEG C insulation 1h, is warming up to 100 DEG C, is incubated 2h, filtering obtains ferric phosphate crude product；
S3, by ferric phosphate crude product add reactor, add distilled water configuration admittedly contain 50%, be warming up to 80 DEG C of agitator treatings
15min, filtering, repeated washing 3 times, PH is close to 7, and washing is completed；
S4,12h will be dried in phosphoric acid iron product and 90 DEG C of baking ovens, you can phosphoric acid iron product.
Product yield is calculated with source of iron and reaches 99%, granularity reaches that 4.2um meets HG/T4701-2014《Battery phosphoric acid
Iron》Industry code requirements, tap density reaches 0.80g/cm3, meets HG/T4701-2014《Battery ferric phosphate》Professional standard
It is required that.
The beneficial effects of the invention are as follows：
1) directly use the oxide of iron powder, pure iron and iron as raw material, the technique that it prepares ferrous phosphate is relatively simple,
Effectively solve phosphate and molysite and enter line replacement reaction and be made to need after ferrous phosphate to asking that the salt of reaction by-product is handled
Topic, substantial amounts of by-product salt is worth relatively low, sales difficulty, also add the energy consumption and artificial, equipment cost of production；
2) performance of ferric phosphate is controlled by high-pressure oxidation process, the performances such as tap density are effectively improved；
3) by by phosphoric acid rectification and purification reuse, effectively reducing material loss, the phosphorus content for reducing sewage is reduced
Sewage disposal difficulty.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (5)
1. a kind of preparation method of ferric phosphate, it is characterised in that preparation method is as follows：
It is prepared by S1, ferrous phosphate：Contain distilled water configuration material in source of iron and phosphoric acid and phosphoric acid mother liquor input reactor, is added admittedly
5%-15%, heating, stirring, reacts 0.5-2h at a temperature of 60-100 DEG C；Filtered again, filtrate is ferrous phosphate mother liquor；
S2, ferric phosphate preparation：By ferrous phosphate and hydrogen peroxide mol ratio 1 in autoclave pressure:0.5-2 ratio is sub- to phosphoric acid
30% hydrogenperoxide steam generator is put into iron mother liquor, 40-60 DEG C of progress synthesis under normal pressure is warming up to, is warming up to 90-120 DEG C and enters horizontal high voltage
Reaction, then filtered, filter residue is ferric phosphate crude product, and filtrate is phosphoric acid mother liquor after rectifying column rectification and purification, and reuse is extremely
Ferrous phosphate preparatory phase；
S3, washing：Ferric phosphate crude product is configured using distilled water, solution contains 5%-50% admittedly, is warming up to 60-80 DEG C of stirring and washes
Wash, repeated washing after filtering；
S4, drying：By the phosphoric acid iron product after the completion of washing in drying 8-12h in 80-100 DEG C of drying box, that is, obtain phosphoric acid
Iron product.
2. a kind of preparation method of ferric phosphate according to claim 1, it is characterised in that source of iron described in S1 be iron powder,
One or more in di-iron trioxide, ferroso-ferric oxide or pure iron.
3. a kind of preparation method of ferric phosphate according to claim 2, it is characterised in that the source of iron is with phosphorylated ligand ratio
1:1.01-1.03。
4. a kind of preparation method of ferric phosphate according to claim 1, it is characterised in that synthesis under normal pressure time described in S2
For 0.5-1h, the reaction under high pressure time is 1-2h.
5. the preparation method of a kind of ferric phosphate according to claim 1, it is characterised in that the agitator treating time is in S3
PH value is close to 7 after 15-30mi n, repeated washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710438654.6A CN107032316A (en) | 2017-06-12 | 2017-06-12 | A kind of preparation method of ferric phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710438654.6A CN107032316A (en) | 2017-06-12 | 2017-06-12 | A kind of preparation method of ferric phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107032316A true CN107032316A (en) | 2017-08-11 |
Family
ID=59540811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710438654.6A Pending CN107032316A (en) | 2017-06-12 | 2017-06-12 | A kind of preparation method of ferric phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107032316A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337189A (en) * | 2017-08-23 | 2017-11-10 | 江西艾德纳米科技有限公司 | The method of ferric phosphate continuous production system and continuous production ferric phosphate |
| CN108609595A (en) * | 2018-05-10 | 2018-10-02 | 湖南雅城新材料有限公司 | Ferric phosphate and its preparation method and application |
| CN110342485A (en) * | 2019-08-06 | 2019-10-18 | 贵州开瑞科技有限公司 | A kind of battery-grade iron phosphate alkali-free formula production method |
| CN110615420A (en) * | 2019-09-17 | 2019-12-27 | 北京科技大学 | Method for preparing iron phosphate from laterite nickel ore leaching slag |
| CN112573497A (en) * | 2020-11-23 | 2021-03-30 | 湖南雅城新材料有限公司 | Method for preparing iron phosphate by using ferric oxide |
| CN114084878A (en) * | 2021-11-18 | 2022-02-25 | 广西诺方储能科技有限公司 | Preparation method for synthesizing iron phosphate by using double iron sources |
| WO2022116702A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464309A (en) * | 2010-11-19 | 2012-05-23 | 河南环宇集团有限公司 | Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide |
| CN105118995A (en) * | 2015-10-14 | 2015-12-02 | 湖南省正源储能材料与器件研究所 | Production method of battery-grade iron phosphate |
| CN106064810A (en) * | 2016-05-31 | 2016-11-02 | 百川化工(如皋)有限公司 | A kind of method preparing iron phosphate |
| CN106064811A (en) * | 2016-05-31 | 2016-11-02 | 百川化工(如皋)有限公司 | A kind of preparation method of ferric phosphate |
-
2017
- 2017-06-12 CN CN201710438654.6A patent/CN107032316A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464309A (en) * | 2010-11-19 | 2012-05-23 | 河南环宇集团有限公司 | Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide |
| CN105118995A (en) * | 2015-10-14 | 2015-12-02 | 湖南省正源储能材料与器件研究所 | Production method of battery-grade iron phosphate |
| CN106064810A (en) * | 2016-05-31 | 2016-11-02 | 百川化工(如皋)有限公司 | A kind of method preparing iron phosphate |
| CN106064811A (en) * | 2016-05-31 | 2016-11-02 | 百川化工(如皋)有限公司 | A kind of preparation method of ferric phosphate |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337189A (en) * | 2017-08-23 | 2017-11-10 | 江西艾德纳米科技有限公司 | The method of ferric phosphate continuous production system and continuous production ferric phosphate |
| CN107337189B (en) * | 2017-08-23 | 2019-09-20 | 江西艾德纳米科技有限公司 | The method of ferric phosphate continuous production system and continuous production ferric phosphate |
| CN108609595A (en) * | 2018-05-10 | 2018-10-02 | 湖南雅城新材料有限公司 | Ferric phosphate and its preparation method and application |
| CN108609595B (en) * | 2018-05-10 | 2020-08-21 | 湖南雅城新材料有限公司 | Iron phosphate and preparation method and application thereof |
| CN110342485A (en) * | 2019-08-06 | 2019-10-18 | 贵州开瑞科技有限公司 | A kind of battery-grade iron phosphate alkali-free formula production method |
| CN110615420A (en) * | 2019-09-17 | 2019-12-27 | 北京科技大学 | Method for preparing iron phosphate from laterite nickel ore leaching slag |
| CN112573497A (en) * | 2020-11-23 | 2021-03-30 | 湖南雅城新材料有限公司 | Method for preparing iron phosphate by using ferric oxide |
| WO2022116702A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate and use thereof |
| CN114084878A (en) * | 2021-11-18 | 2022-02-25 | 广西诺方储能科技有限公司 | Preparation method for synthesizing iron phosphate by using double iron sources |
| CN114084878B (en) * | 2021-11-18 | 2023-07-21 | 广西诺方储能科技有限公司 | Preparation method for synthesizing ferric phosphate by using double iron sources |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107032316A (en) | A kind of preparation method of ferric phosphate | |
| CN106064811B (en) | A kind of preparation method of ferric phosphate | |
| CN106064810A (en) | A kind of method preparing iron phosphate | |
| CN102491302B (en) | Battery-grade anhydrous iron phosphate and preparation method thereof | |
| CN104447564B (en) | High-purity 4,5-dicyano-2-trifluoromethyl imidazoles and the preparation method of salt thereof | |
| WO2019200557A1 (en) | Preparation method for iron phosphate | |
| CN103825024B (en) | A kind of battery-grade iron phosphate and preparation method thereof | |
| CN104518217A (en) | Battery grade iron and manganese phosphate and preparation method thereof | |
| CN103606694A (en) | Preparation method for commercial vanadium battery electrolyte | |
| CN106586995B (en) | A kind of method of efficient process lithium phosphate reclaimed materials | |
| CN104037413A (en) | Preparation method of positive electrode material (carbon-coated iron-manganese-lithium phosphate) of lithium ion battery | |
| CN107857243A (en) | The method that titanium white by product thing ferrous sulfate prepares LITHIUM BATTERY superfine iron phosphate | |
| CN105024072A (en) | Method for preparing ferric pyrophosphate used for lithium ion battery by utilizing iron-bearing raffinate | |
| CN104051797B (en) | A kind of energy-conservation charge technology that is internalized into | |
| CN103539168B (en) | The purification process of lithium hexafluoro phosphate | |
| CN110661052A (en) | Production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder | |
| CN106117218A (en) | A kind of preparation method of Tetrafluoroboric acid spiro quaternary ammonium salt | |
| CN105870532B (en) | A method of preparing cobaltosic oxide/carbon composite using cobalt acid lithium old and useless battery positive electrode | |
| CN107863531A (en) | A kind of method that anode material for lithium-ion batteries is prepared using siderite | |
| CN104064795A (en) | Preparation method of high-purity vanadyl sulfate electrolyte | |
| JPS60148068A (en) | Manufacture of electrolyte in redox cell | |
| CN102963937B (en) | A kind of refining method of by-product Manganse Dioxide | |
| CN103137981B (en) | Preparation method for anhydrous lithium iodide | |
| CN112591726A (en) | Preparation method of iron phosphate | |
| CN105280963A (en) | Acid-free external formation method of lead-acid storage battery and lead-acid storage battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170811 |
|
| RJ01 | Rejection of invention patent application after publication |