CN106981656A - A kind of preparation method of LITHIUM BATTERY iron manganese phosphate - Google Patents
A kind of preparation method of LITHIUM BATTERY iron manganese phosphate Download PDFInfo
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- CN106981656A CN106981656A CN201710336682.7A CN201710336682A CN106981656A CN 106981656 A CN106981656 A CN 106981656A CN 201710336682 A CN201710336682 A CN 201710336682A CN 106981656 A CN106981656 A CN 106981656A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of LITHIUM BATTERY iron manganese phosphate.Comprise the following steps：Source of iron, manganese source, surfactant, carbon nano tube paste are mixed to prepare slurry a in a kettle., microcosmic salt, oxidant are mixed to prepare phosphorus solution b and added and reacts obtained crystal seed c in reactor with slurry a progress；Source of iron, manganese source mixed solution d and microcosmic salt, oxidant mixed solution e are configured, c and d is stirred in a kettle., e is added and is reacted, transition crystallization, filtering, washing, drying, crushing can be prepared by LITHIUM BATTERY iron manganese phosphate.The preparation method has（Iron+manganese）/ phosphorus ratio, granularity and more controllable than surface；Technological process is simple, be easy to industrialization；Porous CNT is further introduced into the case where adding surfactant, promotes granularity and the homogeneity of conductive network, effectively shortens ion transport channel, conductance is improved, is the splendid persursor material for manufacturing iron manganese phosphate for lithium.
Description
Art
The invention belongs to lithium ion battery material production technical field, it is related to a kind of battery by crystal seed synthetic technology
The preparation method of level iron manganese phosphate.
Background technology
The phosphate-based positive electrode of new olivine-type structure is in terms of security performance and cycle life better than biography
The Layered Structural Positive Electrode Materials (such as cobalt acid lithium, lithium nickelate, ternary material) of system, its representative materials LiFePO4 is by academia
With industrial circle is widely studied confirms, and be widely used in the fields such as power and energy-storage battery.However, LiFePO4 3.4V
(vs.Li/Li+) current potential limits the lifting of battery energy density, therefore lithium iron phosphate dynamic battery market development is limited.With
LiFePO4 is compared, and iron manganese phosphate for lithium has~4.0V high potential and almost identical theoretical capacity, is played in equivalent capability
Under conditions of, the energy density of iron manganese phosphate lithium battery will improve~20% or so than ferric phosphate lithium cell.Iron manganese phosphate for lithium is just
The manufacture of pole material, generally uses main raw material (LITHIUM BATTERY oxalic acid ferromanganese or iron manganese phosphate), lithium salts and microcosmic salt both at home and abroad at present
Mixing carries out solid phase method production, and other method such as sol-gel process, liquid-phase precipitation method have the disadvantage impurity content height, electrochemistry
Can be poor.Therefore, the quality of iron manganese phosphate for lithium combination property manufactures used main raw material with it much relations.Before synthesis
The method for driving body iron manganese phosphate is more：(1) Liu Guanwei etc. (application number 201410054941.3, the A of notification number CN 104852037)
Coat the iron manganese phosphate presoma of the rich manganese of the rich iron of method synthetic surface-core of synthesis admittedly using liquid, the shortcoming of this method be iron,
Manganese homogeneity and crystal formation are difficult to control to, and industrialization difficulty is big；(2) (application number 201410506146.3, the notification number CN such as Chen Jinghua
105514422 A) oxalic acid ferromanganese presoma is prepared using liquid-phase precipitation method, the shortcoming of this method is that impurity content is difficult to control to,
The lithium iron manganese phosphate anode material tap density that oxalic acid ferromanganese presoma, lithium salts etc. are prepared after high-temperature calcination is relatively low, holds
Amount plays relatively low.(3) Yang Zhikuan (application number 201510027348.4, the A of notification number CN 104518217) uses liquid-phase precipitation method
Iron manganese phosphate presoma is prepared, the shortcoming of this method is preparation time up to approximately 48h, and temperature is in 100-250 DEG C, production efficiency
It is low, high energy consumption；(4) Huang Changjing (application number 201510536059.7, the A of notification number CN 105244497) is mixed using alcohol-water
Condensing reflux heating prepares iron manganese phosphate presoma under system, and the shortcoming of this method is, product high to equipment safety coefficient requirements
Granularity is uncontrollable；(5) Cheng Lulu etc. (application number 201510998857.1, the A of notification number CN 105449207) uses liquid-phase precipitation
Method prepares iron manganese phosphate presoma, and the shortcoming of this method is a maximum of about of 150 DEG C of synthesis temperature, and energy consumption is higher, and single washing is removed
Miscellaneous mode is difficult to control to impurity content, and the stability of product is not high.
The content of the invention
The present invention overcomes existing technology of preparing deficiency there is provided a kind of preparation method of LITHIUM BATTERY iron manganese phosphate, utilizes the system
Iron manganese phosphate (iron+manganese)/phosphorus ratio that Preparation Method is obtained, granularity and more controllable than surface；Technological process is simple, be easy to industrialization；
Porous CNT is further introduced into the case of adding surfactant, promotes granularity and the homogeneity of conductive network, has
Effect shortens ion transport channel, improves conductance.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of method of LITHIUM BATTERY iron manganese phosphate, comprises the following steps：
(1) in a kettle., source of iron, manganese source, surfactant, carbon nano tube paste are mixed to prepare slurry a, wherein table
Face activating agent accounts for the 0.2-1.0% of gross mass；Source of iron concentration 0.025-0.1mol/L, manganese source concentration 0.1-0.4mol/L；Carbon is received
Mitron slurry accounts for the 0.2-1.5% of gross mass；
(2) oxidant and 0.13-0.5mol/L microcosmic salts are mixed to prepare into solution b to add in reactor, risen with slurry a
Warm 85-95 DEG C and ultrasonic oscillation is carried out, reacted 2-8 hour, obtained crystal seed c；
(3) configuration iron, manganese mixed solution d, wherein source of iron concentration 0.2-1.5mol/L, manganese source concentration 0.8-6.0mol/L；
Configure the mixed solution e of oxidant and 1-7.5mol/L microcosmic salts；
(4) c and d is stirred in a kettle., adds e and carry out 85-95 DEG C of heating and carry out ultrasonic oscillation, instead
Answer 2-8 hours, add phosphoric acid and carry out transition crystallization 2-6 hours, LITHIUM BATTERY manganese phosphate can be obtained by filtering, wash, dry and crushing
Iron.
Wherein described source of iron is included in ferrous sulfate, ferrous nitrate, frerrous chloride, ferric nitrate, ferric sulfate, ferric acetate
One or more kinds of combinations.
Wherein described manganese source includes group more than one or both of manganese sulfate, manganese nitrate, manganese chloride, manganese acetate
Close.
Wherein described surfactant includes cetyl trimethylammonium bromide, dodecyl sodium sulfate, polyethylene pyrrole
Combination more than one or both of pyrrolidone.
Wherein described carbon nano tube paste be water system, purity 99.8%, caliber be 7~11nm, 10~15nm, 13~
Combination more than one or both of series such as 25nm, 20-30nm, 30-50nm.
Wherein described phosphate includes ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, phosphoric acid
Combination more than one or both of potassium dihydrogen, dipotassium hydrogen phosphate, sodium phosphate, potassium phosphate.
Wherein described oxidant includes one in hydrogen peroxide, nitric acid, sodium hypochlorite, postassium hypochlorite, sodium chlorate, potassium chlorate
Plant or two or more combinations.
Wherein described phosphoric acid is mass volume ratio 50-85% phosphoric acid.
The beneficial effects of the invention are as follows：
By using crystal seed, the CNT of different pore size, surfactant collaboration effectively control particle diameter 3.5um≤D50
≤ 15.0um and than surface 30.0-100.0m2/g；(iron+manganese)/phosphorus ratio is in 0.97-1.00；By introducing carbon nanotube conducting agent
With the insertion of iron manganese phosphate particle height homogeneity, effectively shorten ion transport channel, improve electrical efficiency；Technological process letter
Singly, it is easy to industrialization, is the splendid persursor material for manufacturing iron manganese phosphate for lithium.
Embodiment
Embodiment 1
A kind of method for preparing LITHIUM BATTERY iron manganese phosphate, comprises the following steps：
In a kettle., by source of iron (ferrous sulfate), manganese source (manganese sulfate), surfactant (cetyl trimethyl bromine
Change ammonium), caliber 7~11nm carbon nano tube pastes be mixed to prepare slurry a, wherein cetyl trimethylammonium bromide accounts for gross mass
0.2%；Ferrous sulfate concentration 0.025mol/L, manganese sulfate concentration 0.1mol/L；Carbon nano tube paste accounts for the 0.2% of gross mass；
Hydrogen peroxide and 0.13mol/L ammonium dihydrogen phosphates are mixed to prepare into solution b to add in reactor, 85 DEG C of heating is carried out simultaneously with slurry a
Ultrasonic oscillation is carried out, is reacted 2 hours, crystal seed c is made；Configure ferrous sulfate, wherein manganese sulfate mixed solution d, source of iron concentration
0.2mol/L, manganese source concentration 0.8mol/L；Configuration hydrogen peroxide is mixed to prepare solution e with 1.0mol/L ammonium dihydrogen phosphates；By c and d
Stir in a kettle., add e and carry out 85 DEG C of heating and carry out ultrasonic oscillation, react 2 hours, add 50% phosphorus
Acid progress transition crystallization 2 hours, filtering, washing, drying and crushing can obtain LITHIUM BATTERY iron manganese phosphate.Measure its (iron+manganese)/phosphorus ratio
0.97, particle diameter 3.5um, specific surface area 100.0m2/g。
Embodiment 2
A kind of method for preparing LITHIUM BATTERY iron manganese phosphate, comprises the following steps：
In a kettle., by source of iron (ferrous nitrate), manganese source (manganese nitrate), surfactant (dodecyl sodium sulfate),
Caliber 10~15nm carbon nano tube pastes are mixed to prepare slurry a, and wherein dodecyl sodium sulfate accounts for the 0.4% of gross mass；Nitric acid
Ferrous iron concentration 0.04mol/L, manganese nitrate concentration 0.16mol/L；Carbon nano tube paste accounts for the 0.5% of gross mass；By nitric acid with
0.2mol/L diammonium hydrogen phosphates are mixed to prepare solution b and added in reactor, carry out 90 DEG C of heating with slurry a and carry out ultrasonic wave shake
Swing, react 3.5 hours, crystal seed c is made；Configure ferrous nitrate, wherein manganese nitrate mixed solution d, source of iron concentration 0.4mol/L, manganese
Source concentration 1.6mol/L；Configuration nitric acid is mixed to prepare solution e with 2.0mol/L diammonium hydrogen phosphates；C and d is stirred in a kettle.
Uniformly, add e to carry out 90 DEG C of heating and carry out ultrasonic oscillation, react 3.5 hours, add the progress transition of 60% phosphoric acid brilliant
Change 3 hours, filtering, washing, drying and crushing can obtain LITHIUM BATTERY iron manganese phosphate.Measure its (iron+manganese)/phosphorus and compare 0.985, particle diameter
6.2um, specific surface area 85.0m2/g。
Embodiment 3
A kind of method for preparing LITHIUM BATTERY iron manganese phosphate, comprises the following steps：
In a kettle., by source of iron (frerrous chloride), manganese source (manganese chloride), surfactant (polyvinylpyrrolidone),
Caliber 13~25nm carbon nano tube pastes are mixed to prepare slurry a, and wherein polyvinylpyrrolidone accounts for the 0.6% of gross mass；Chlorination
Ferrous iron concentration 0.065mol/L, manganese chloride concentration 0.26mol/L；Carbon nano tube paste accounts for the 0.75% of gross mass；By hypochlorous acid
Sodium is mixed to prepare solution b with 0.33mol/L sodium phosphates and added in reactor, carries out 93 DEG C of heating with slurry a and carries out ultrasonic wave
Concussion, reacts 4 hours, and crystal seed c is made；Configure frerrous chloride, wherein manganese chloride mixed solution d, source of iron concentration 0.6mol/L, manganese
Source concentration 2.4mol/L；Configuration nitric acid is mixed to prepare solution e with 3.0mol/L sodium phosphates；C and d are stirred in a kettle.
It is even, add e and carry out 95 DEG C of heating and carry out ultrasonic oscillation, react 4 hours, add 70% phosphoric acid and carry out transition crystallization 4
Hour, filtering, washing, drying and crushing can obtain LITHIUM BATTERY iron manganese phosphate.Measure its (iron+manganese)/phosphorus and compare 0.991, particle diameter
8.5um, specific surface area 62.0m2/g。
Embodiment 4
A kind of method for preparing LITHIUM BATTERY iron manganese phosphate, comprises the following steps：
In a kettle., by source of iron (frerrous chloride and iron chloride), manganese source (manganese sulfate and manganese nitrate), surfactant
(dodecyl sodium sulfate and polyvinylpyrrolidone), caliber 20-30nm carbon nano tube pastes are mixed to prepare slurry a, wherein ten
Dialkyl sulfonates account for the 0.85% of gross mass with polyvinylpyrrolidone；Frerrous chloride and ferric chloride concn 0.08mol/L, sulphur
Sour manganese and manganese nitrate concentration 0.32mol/L；Carbon nano tube paste accounts for the 0.9% of gross mass；By postassium hypochlorite and 0.45mol/L phosphorus
Acid dihydride potassium is mixed to prepare solution b and added in reactor, carries out 95 DEG C of heating with slurry a and carries out ultrasonic oscillation, reaction 5 is small
When, crystal seed c is made；Configure frerrous chloride, manganese sulfate mixed solution d, wherein source of iron concentration 1.0mol/L, manganese source concentration
4.0mol/L；Configuration hydrogen peroxide is mixed to prepare solution e with 5.0mol/L potassium dihydrogen phosphates；C and d are stirred in a kettle.
It is even, add e and carry out 95 DEG C of heating and carry out ultrasonic oscillation, react 5 hours, add 75% phosphoric acid and carry out transition crystallization 5
Hour, filtering, washing, drying and crushing can obtain LITHIUM BATTERY iron manganese phosphate.Measure its (iron+manganese)/phosphorus and compare 0.995, particle diameter
11.5um, specific surface area 41.5m2/g。
Embodiment 5
A kind of method for preparing LITHIUM BATTERY iron manganese phosphate, comprises the following steps：
In a kettle., by source of iron (ferric sulfate), manganese source (manganese nitrate), surfactant (cetyl trimethyl bromination
Ammonium and polyvinylpyrrolidone), caliber 30-50nm carbon nano tube pastes be mixed to prepare slurry a, wherein cetyl trimethyl bromine
Change ammonium and account for the 1.0% of gross mass with polyvinylpyrrolidone；Sulfuric acid concentration of iron 0.1mol/L, manganese nitrate concentration 0.4mol/L；Carbon
Nanotube slurry accounts for the 1.5% of gross mass；Potassium chlorate and 0.5mol/L diammonium hydrogen phosphates are mixed to prepare solution b and add reactor
In, carry out 90 DEG C of heating with slurry a and carry out ultrasonic oscillation, react 8 hours, crystal seed c is made；Configure iron chloride, manganese sulfate
Mixed solution d, wherein source of iron concentration 1.5mol/L, manganese source concentration 6.0mol/L；Configure nitric acid and 7.5mol/L potassium dihydrogen phosphates
It is mixed to prepare solution e；C and d is stirred in a kettle., e is added and carries out 95 DEG C of heating and carry out ultrasonic oscillation, instead
Answer 8 hours, add 80% phosphoric acid and carry out transition crystallization 5 hours, LITHIUM BATTERY manganese phosphate can be obtained by filtering, wash, dry and crushing
Iron.Measure its (iron+manganese)/phosphorus and compare 0.997, particle diameter 15.0um, specific surface area 30.0m2/g。
Embodiment 6
A kind of method for preparing LITHIUM BATTERY iron manganese phosphate, comprises the following steps：
In a kettle., by source of iron (ferric acetate), manganese source (manganese acetate), surfactant (cetyl trimethyl bromination
Ammonium), caliber 7~11nm/30-50nm carbon nano tube pastes be mixed to prepare slurry a, wherein cetyl trimethylammonium bromide is accounted for always
The 0.9% of quality；Acetic acid concentration of iron 0.07mol/L, manganese acetate concentration 0.28mol/L；Carbon nano tube paste accounts for gross mass
0.95%；Hydrogen peroxide and 0.4mol/L ammonium dihydrogen phosphates are mixed to prepare into solution b to add in reactor, heated up with slurry a
88 DEG C and ultrasonic oscillation is carried out, reacted 7 hours, crystal seed c is made；Configure ferrous sulfate, wherein manganese nitrate mixed solution d, iron
Source concentration 1.1mol/L, manganese source concentration 4.5mol/L；Configuration nitric acid is mixed to prepare solution e with 5.6mol/L sodium dihydrogen phosphates；By c
Stirred in a kettle. with d, add e and carry out 90 DEG C of heating and carry out ultrasonic oscillation, react 6.5 hours, add
85% phosphoric acid carries out transition crystallization 6 hours, and LITHIUM BATTERY iron manganese phosphate can be obtained by filtering, wash, dry and crushing.Measure its (iron+
Manganese)/phosphorus compares 1.00, particle diameter 5.8um, specific surface area 37.5m2/g。
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, technical side of the those of ordinary skill in the art to the present invention
In various modifications and improvement that case is made, the protection domain that claims of the present invention determination all should be fallen into.
Claims (8)
1. a kind of preparation method of LITHIUM BATTERY iron manganese phosphate, it is characterised in that comprise the following steps：
（1）In a kettle., source of iron, manganese source, surfactant, carbon nano tube paste are mixed to prepare slurry a, wherein surface is lived
Property agent accounts for the 0.2-1.0% of gross mass；Source of iron concentration 0.025-0.1 mol/L, manganese source concentration 0.1-0.4mol/L；CNT
Slurry accounts for the 0.2-1.5% of gross mass；
（2）Oxidant and 0.13-0.5mol/L microcosmic salts are mixed to prepare into solution b to add in reactor, heated up with slurry a
85-95 DEG C and ultrasonic oscillation is carried out, reacted 2-8 hour, obtained crystal seed c；
（3）Configure iron, manganese mixed solution d, wherein source of iron concentration 0.2-1.5 mol/L, manganese source concentration 0.8-6.0mol/L；Configuration
The mixed solution e of oxidant and 1-7.5 mol/L microcosmic salts；
（4）C and d is stirred in a kettle., e is added and carries out 85-95 DEG C of progress ultrasonic oscillation of heating, react 2-8
Hour, add phosphoric acid progress transition crystallization 2-6 hours, filtering, washing, drying and crushing can obtain LITHIUM BATTERY iron manganese phosphate.
2. a kind of preparation method of LITHIUM BATTERY iron manganese phosphate according to claim 1, it is characterised in that：Described step
（1）Or（3）In source of iron include ferrous sulfate, ferrous nitrate, frerrous chloride, ferric nitrate, ferric sulfate, ferric trichloride in one kind
Or two or more combinations.
3. a kind of preparation method of LITHIUM BATTERY iron manganese phosphate according to claim 1, it is characterised in that：Described step
（1）Or（3）In manganese source include combination more than one or both of manganese sulfate, manganese nitrate, manganese chloride, manganese acetate.
4. a kind of preparation method of LITHIUM BATTERY iron manganese phosphate according to claim 1, it is characterised in that：Described step
（1）In surfactant include cetyl trimethylammonium bromide, dodecyl sodium sulfate, polyvinylpyrrolidone in one
Plant or two or more combinations.
5. a kind of preparation method of LITHIUM BATTERY iron manganese phosphate according to claim 1, it is characterised in that：Described step
（1）In carbon nano tube paste be that water system, purity 99.8%, caliber are 7 ~ 11nm, 10 ~ 15nm, 13 ~ 25nm, 20-30nm, 30-
Combination more than one or both of 50nm series.
6. a kind of preparation method of LITHIUM BATTERY iron manganese phosphate according to claim 1, it is characterised in that：Described step
（2）Or（3）In microcosmic salt include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, phosphorus
Combination more than one or both of sour hydrogen dipotassium, sodium phosphate, potassium phosphate.
7. a kind of preparation method of LITHIUM BATTERY iron manganese phosphate according to claim 1, it is characterised in that：Described step
（2）Or（3）In oxidant include hydrogen peroxide, nitric acid, sodium hypochlorite, postassium hypochlorite, sodium chlorate, potassium chlorate in one kind or two
Plant the combination of the above.
8. a kind of preparation method of LITHIUM BATTERY iron manganese phosphate according to claim 1, it is characterised in that：Described step
（4）In phosphoric acid be mass volume ratio 50-85% phosphoric acid.
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| CN107706380A (en) * | 2017-09-27 | 2018-02-16 | 郴州博太超细石墨股份有限公司 | A kind of method that phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate |
| CN114229814A (en) * | 2021-12-02 | 2022-03-25 | 荆门市格林美新材料有限公司 | Production method of lithium iron phosphate precursor |
| CN115849324A (en) * | 2022-11-23 | 2023-03-28 | 中国科学院深圳先进技术研究院 | Lithium iron manganese phosphate precursor and preparation method and application thereof |
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