CN107697899A - Preparation method, lithium ferric manganese phosphate, cell positive material and the secondary cell of battery-grade iron phosphate manganese - Google Patents
Preparation method, lithium ferric manganese phosphate, cell positive material and the secondary cell of battery-grade iron phosphate manganese Download PDFInfo
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
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- 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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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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Abstract
The invention discloses the preparation method of battery-grade iron phosphate manganese, lithium ferric manganese phosphate, cell positive material and secondary cell, particularly discloses a kind of method that oxidation precipitation reaction prepares battery-grade iron phosphate manganese under single water solution system, and this method includes：The salt-mixture of manganous salt and divalent iron salt is dissolved in water, the pH regulators prepared are added by peristaltic pump while stirring into reactor, the pH value of reaction system is adjusted to 7.5~12.0, continues to stir after terminating；Oxidant is added into reactor again, continues to stir after terminating；After temperature reaches 60~165 DEG C in question response kettle, soluble sources solution is added with peristaltic pump, is reacted 2~8 hours, reaction terminates rear phosphoric acid ferrimanganic slurry and naturally cools to room temperature, through washing, filtering, dry, obtains finished product MnxFe1‑xPO4·yH2O, this method is pollution-free, technique is simple, and yield is high, is suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, especially relates to a kind of single aqueous liquid
The method that the lower oxidation-precipitation reaction of system prepares battery-grade iron phosphate manganese.
Background technology
Lithium ferric manganese phosphate battery material have with LiFePO4 identical specific capacity (theoretical capacity 170mAh/g), but have
There is higher voltage platform (4.1V), can be in LiFePO4On the basis of improve about 20% energy density.Based on above two
Advantage, lithium ferric manganese phosphate battery material have obtained extensive concern and research.Reasonable adjustment Mn and Fe mol ratio, prepare height
The phosphoric acid ferrimanganic presoma of activity is the key for preparing high-energy-density and the lithium ferric manganese phosphate battery material of high conductivity.
The preparation method of lithium ferric manganese phosphate battery material and presoma, many relevant reports have been seen at present.Prepare phosphorus at present
The method of sour ferrimanganic lithium mainly has high temperature solid-state method, sol-gal process and coprecipitation.Wherein high temperature solid-state method use is more wide
It is general, also relatively it is adapted to industrialized production.But solid phase reaction is difficult to control the nucleation rate and thing phase ion diffusion speed of product phase
Rate, therefore the homogeneity of product of the lithium ferric manganese phosphate synthesized is poor, granule-morphology is uneven, broad particle distribution, and entirely
More exhaust emission, mainly NH can be produced during high temperature solid state reaction3、CO2Deng.To solve disadvantages mentioned above, use is coprecipitated
Shallow lake method, which prepares phosphoric acid ferrimanganic presoma, turns into the emphasis of people's research.As China Patent Publication No. discloses for CN104518217A
A kind of preparation method of battery-grade iron phosphate manganese, using oxidation-coprecipitation method under hydro-thermal, source of iron, manganese source, phosphorus source are placed in
In reactor, surfactant and nitric acid are then added, the nitric acid of addition is used to aoxidize Mn respectively at 100~250 DEG C2+With
Fe2+For Mn3+And Fe3+, then with PO4 3-With reference to preparing the Mn with the crystallization waterxFe1-xPO4·yH2O.Although prepared by this method
The phosphoric acid ferrimanganic that iron mixes with manganese atom rank is gone out, but the nitric acid added aoxidizes Mn at 100~250 DEG C2+And Fe2+Mistake
Cheng Zhong, substantial amounts of nitrous oxides exhaust gas can be discharged, seriously pollute environment, and reaction temperature is also higher.China Patent Publication No.
CN105449207A discloses a kind of preparation method and product of phosphoric acid ferrimanganic, and source of iron, manganese source, phosphorus source are placed in reactor,
Oxidant and dispersant are added, is reacted 2~24 hours at 50~150 DEG C, through washing, filtering, dry, prepares MnxFe1- xPO4·yH2O.But there is also addition nitric acid or sodium nitrate to make oxidant, discharge nitrogen oxides pollution and building-up process in also
The problems such as dispersant absolute ethyl alcohol need to be added.China Patent Publication No. CN105244497A discloses phosphoric acid ferrimanganic intermediate and phosphorus
The preparation method of sour ferrimanganic lithium/carbon composite material, it is main material in alcohol-water mixed system using manganese nitrate, ferric nitrate and phosphoric acid
Lower condensing reflux heating prepares phosphoric acid ferrimanganic intermediate, is once mixed by using lithium source, carbon source and phosphoric acid ferrimanganic intermediate, use
The technique for expecting step sintering, has prepared lithium ferric manganese phosphate/carbon composite of excellent performance.This method is in order to prevent metal salt
Oxidation, reactor also needs to be passed through inert gas shielding before charging, and simultaneous reactions system is alcohol-water mixed system, phosphoric acid with
The mol ratio n of doping metals M saltPhosphoric acid/n(Mn+Fe+M)=2~4, the volume ratio V of ethanol and phosphoric acidEthanol/VPhosphoric acid=3.5~4, second be present
The problems such as alcohol, phosphoric acid dosage are excessive, and cost of material is high, to reduce the loss of solvent, it is necessary to heated using condensing reflux, technique
Complexity, be not suitable for industrialized production.
The content of the invention
It is an object of the present invention in view of the above-mentioned problems, offer one kind is pollution-free, technique is simple, yield is high, is suitable for work
The preparation method of the battery-grade iron phosphate manganese of industry metaplasia production.Oxidation-precipitation reaction under single water solution system, 60~165
At DEG C, react 2~8 hours, you can reaction is complete, does not have any waste gas to discharge in oxidizing process, environmentally friendly, and product
High income, manganese, iron yield are more than 99.5%, and ferric phosphate manganese product purity is high, and impurity content is low, Na≤100ppm, and S≤
100ppm, and the ferric phosphate manganese product of different Mn/Fe mol ratios according to the demand in market, can be prepared.
The chemical formula of described phosphoric acid ferrimanganic is MnxFe1-xPO4·yH2O, 0.5≤x≤0.8, y value are 0 or 1.Manganese, iron
Conjunction valence state is positive trivalent.
To achieve the above object, the technical solution adopted by the present invention is as follows：
The method that the present invention prepares phosphoric acid ferrimanganic using oxidation-depositing technology under single water solution system, this method include
Step is as follows：
1) salt-mixture of manganous salt and divalent iron salt is added in reactor, adds water, being stirred at room temperature makes its complete
Dissolving, it is configured to the aqueous solution of manganous salt that concentration is respectively 0.2~4mol/L and divalent iron salt, preferably 0.2~2mol/
L；
2) the pH regulators prepared are added by peristaltic pump while stirring into reactor, adjusts the pH of reaction system
Value continues stirring 10~20 minutes to 7.5~12.0 after terminating；
3) oxidant is added with 30~100r/min charging rate by peristaltic pump into reactor, continues to stir after terminating
Mix 20~60 minutes；
4) after temperature reaches 60~165 DEG C in question response kettle, soluble sources solution is added with peristaltic pump, reaction 2~8 is small
When, reaction terminates rear phosphoric acid ferrimanganic slurry and naturally cools to room temperature, through washing, filtering, dry, obtains finished product MnxFe1- xPO4·yH2O。
More specifically, described manganous salt is one kind in manganese sulfate, Mn nitrate, protochloride manganese, acetic acid Asia manganese
It is or a variety of；
Described divalent iron salt is the one or more in ferrous sulfate, ferrous nitrate, frerrous chloride；
Described pH regulators are the one or more in sodium hydroxide, ammoniacal liquor, sodium acetate, ammonium acetate；
Described oxidant is sodium peroxide, hydrogen peroxide, one or more in ozone, and wherein oxidant and manganese and iron rubs
That ratio, oxidant/(Mn+Fe)=1~4, preferably 1~2；
Described phosphorus source is phosphoric acid, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, the one or more in ammonium phosphate, phosphorus source with
The mol ratio of manganese and iron is P/ (Mn+Fe)=1.1~2, preferably 1.1~1.6；
It is Mn/Fe=1~4 by the raw materials components mole ratio for adjusting manganese salt and molysite, different Mn/Fe mol ratios can be obtained
Phosphoric acid ferrimanganic MnxFe1-xPO4·yH2O products, 0.5≤x≤0.8, y values are 0 or 1.
The method of the present invention for preparing phosphoric acid ferrimanganic using oxidation-depositing technology under single water solution system, may be used also
With including following method and steps：
1) manganous salt is added in reactor, adds water, being stirred at room temperature is completely dissolved it, is configured to concentration and is
The aqueous solution of 0.2~4mol/L manganous salt, preferably 0.2~2mol/L；
2) the pH regulators prepared are added by peristaltic pump while stirring into reactor, adjusts the pH of reaction system
Value continues stirring 10~20 minutes to 7.5~12.0 after terminating；
3) oxidant is added with 30~100r/min charging rate by peristaltic pump into reactor, continues to stir after terminating
Mix 20~60 minutes；
4) ferric salt solution prepared is added by peristaltic pump into reactor, continues 30 points of stirring after terminating
Clock；Ferric salt solution concentration is 0.2~4mol/L, preferably 0.2~2mol/L；
5) after temperature reaches 60~165 DEG C in question response kettle, a certain amount of soluble sources solution is added with peristaltic pump, instead
Answer 2~8 hours, reaction terminates rear phosphoric acid ferrimanganic slurry and naturally cools to room temperature, through washing, filtering, dry, obtains finished product
MnxFe1-xPO4·yH2O。
More specifically, described manganous salt is one kind in manganese sulfate, Mn nitrate, protochloride manganese, acetic acid Asia manganese
It is or a variety of；
Described pH regulators are the one or more in sodium hydroxide, ammoniacal liquor, sodium acetate, ammonium acetate；
Described oxidant is sodium peroxide, hydrogen peroxide, one or more in ozone, and wherein oxidant and manganese and iron rubs
That ratio, oxidant/(Mn+Fe)=1~4, preferably 1~2；
Described trivalent iron salt is the one or more in ferric sulfate, ferric nitrate, iron chloride；
Described phosphorus source is phosphoric acid, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, the one or more in ammonium phosphate, phosphorus source with
The mol ratio of manganese and iron is P/ (Mn+Fe)=1.1~2, preferably 1.1~1.6；
It is Mn/Fe=1~4 by the raw materials components mole ratio for adjusting manganese salt and molysite, different Mn/Fe mol ratios can be obtained
Phosphoric acid ferrimanganic MnxFe1-xPO4·yH2O products, 0.5≤x≤0.8, y values are 0 or 1.
Further, the invention further relates to ferric phosphate manganese product prepared by any of the above-described methods described.
Further, the invention further relates to a kind of lithium ferric manganese phosphate, the ferric phosphate prepared by any of the above-described methods described
Manganese and lithium compound synthesis form.Wherein, lithium compound is the lithium salts that lithium ferric manganese phosphate can be synthesized with phosphoric acid ferrimanganic, preferably
For the one or more in lithium carbonate, lithium hydroxide, lithium acetate.
Further, the invention further relates to a kind of cell positive material, the cell positive material is used through battery electricity
The positive electrode of the secondary cell of discharge and recharge is repeated in pole, and method described above is synthesized based on the lithium ferric manganese phosphate formed
Body.
Further, the invention further relates to a kind of secondary cell, it is made with above-mentioned cell positive material.
The preparation method of the present invention has the characteristics that compared with existing phosphoric acid ferrimanganic preparation method：
1) the inventive method solves during oxidation-coprecipitation phosphoric acid ferrimanganic manganous salt and divalent iron salt in oxygen
Make oxidant using nitric acid or nitrate in change, discharge nitrous oxides exhaust gas, the problem of environmental pollution, this method uses wiper ring
Guarantor's type oxidant, no exhaust emission are environment-friendly；
2) the inventive method oxidation-precipitation method prepare phosphoric acid ferrimanganic, and wherein oxidizing process is carried out under alkaline environment,
First pass through pH regulators and system pH is adjusted to 7.5~12.0, then add oxidant, by manganous salt and divalent iron salt oxygen
Trivalent manganese salt and trivalent iron salt are melted into, and other oxidation-precipitation method prepare phosphoric acid ferrimanganic, its oxidizing process is extremely acid body
Carried out in system；
3) the inventive method replaces organic solvent-aqueous systems with single water solution system, and organic solvent-aqueous systems exist
Need to add substantial amounts of organic solvent in building-up process, in order to reduce the loss of solvent, also need the mode of heating using condensing reflux
Deng therefore, the inventive method simplifies technological process, more suitable for industrialized production；
4) can be according to the different demands in market, by adjusting the raw material additional proportion of manganese salt and molysite, raw materials components mole ratio is
Mn/Fe=1~4, the phosphoric acid ferrimanganic (Mn of different Mn/Fe mol ratios can be obtainedxFe1-xPO4·yH2O) product, 0.5≤x≤
0.8, y value is 0 or 1；
5) manganese of the inventive method, iron rate of deposition are up to more than 99.5%, and ferric phosphate manganese product purity is high, major impurity content
S is less than 200ppm, and Na contents are less than 100ppm.
Embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1
75.00g sulfuric acid monohydrates Asia manganese (0.4437mol) and 30.84g ferrous sulfate heptahydrates (0.1109mol) are weighed, is dissolved
In 200mL water, the sodium hydroxide solution that 100mL concentration is 10mol/L is added by peristaltic pump while stirring
(1.0000mol), adjustment system pH to 8.51, continue stirring 15 minutes after end to be added, then while stirring by compacted
Dynamic pump adds 60mL mass concentrations as 30% hydrogen peroxide (0.5876mol), reaction to be oxidized using 50r/min charging rate
Continue stirring 30 minutes after end, reactor is then heated to 85 DEG C, then add the phosphoric acid that 45mL mass concentrations are 85%
(0.6557mol), react 5 hours, reaction terminates rear slurry and naturally cools to room temperature, through washing, filtering, dry, obtains final
Phosphoric acid ferrimanganic (one crystallization water of band) product, its chemical formula is Mn0.8Fe0.2PO4·H2O。
Embodiment 2
75.00g sulfuric acid monohydrates Asia manganese (0.4437mol) and 52.87g ferrous sulfate heptahydrates (0.1902mol) are weighed, is dissolved
In 300mL water, the sodium hydroxide solution that 115mL concentration is 10mol/L is added by peristaltic pump while stirring
(1.1500mol), adjustment system pH to 8.98, continue stirring 15 minutes after end to be added, then while stirring by compacted
Dynamic pump adds 68mL mass concentrations as 30% hydrogen peroxide (0.6660mol), reaction to be oxidized using 80r/min charging rate
Continue stirring 30 minutes after end, reactor is then heated to 85 DEG C, then add the phosphoric acid that 51mL mass concentrations are 85%
(0.7431mol), react 6 hours, reaction terminates rear slurry and naturally cools to room temperature, through washing, filtering, dry, obtains final
Phosphoric acid ferrimanganic (one crystallization water of band) product, its chemical formula is Mn0.7Fe0.3PO4·H2O。
Embodiment 3
75.00g sulfuric acid monohydrates Asia manganese (0.4437mol) and 82.24g ferrous sulfate heptahydrates (0.2958mol) are weighed, is dissolved
In 400mL water, the sodium hydroxide solution that 135mL concentration is 10mol/L is added by peristaltic pump while stirring
(1.3500mol), adjustment system pH to 8.64, continue stirring 15 minutes after end to be added, then side stirring passes through wriggling
Pump adds 80mL mass concentrations as 30% hydrogen peroxide (0.7835mol) using 30r/min charging rate, reaction knot to be oxidized
Continue stirring 30 minutes after beam, reactor is then heated to 85 DEG C, then add the phosphoric acid that 60mL mass concentrations are 85%
(0.8743mol), react 5.5 hours, reaction terminates rear slurry and naturally cools to room temperature, through washing, filtering, dry, obtains most
Whole phosphoric acid ferrimanganic (one crystallization water of band) product, its chemical formula is Mn0.6Fe0.4PO4·H2O。
Embodiment 4
Weigh the Mn nitrate solution (0.3984mol) that 100mL concentration is 47.62%, and 27.68g ferrous sulfate heptahydrates
(0.0996mol) is dissolved in 200mL water, adds the sodium hydroxide that 115mL concentration is 10mol/L by peristaltic pump while stirring
Solution (1.1500mol), adjustment system pH to 11.53, continue stirring 10 minutes after end to be added, then lead to while stirring
Cross peristaltic pump and 60mL mass concentrations are added as 30% hydrogen peroxide (0.5876mol) using 100r/min charging rate, treat oxygen
Change after reaction terminates and continue stirring 45 minutes, reactor is then heated to 90 DEG C, it is 85% then to add 55mL mass concentrations
Phosphoric acid (0.8014mol), react 6 hours, reaction terminates rear slurry and naturally cools to room temperature, through washing, filtering, drying, obtains
To final phosphoric acid ferrimanganic (one crystallization water of band) product, its chemical formula is Mn0.8Fe0.2PO4·H2O。
Embodiment 5
The Mn nitrate solution (0.3984mol) that 100mL concentration is 47.62% is weighed, and adds 100 water and is well mixed,
The sodium hydroxide solution (1.0000mol) that 100mL concentration is 10mol/L, adjustment system pH are added by peristaltic pump while stirring
Value continues stirring 10 minutes, then while stirring by peristaltic pump with 50r/min charging speed to 11.08 after end to be added
Degree adds the hydrogen peroxide (0.5876mol) that 60mL mass concentrations are 30%, and reaction to be oxidized continues stirring 60 minutes after terminating,
Then the nine water iron nitrate solutions (0.0996mol) that 50mL concentration is 1.99mol/L are added into system, is well mixed 30 points of stirring
Clock, reactor is then heated to 115 DEG C, then adds the phosphoric acid (0.6557mol) that 45mL mass concentrations are 85%, reaction 6
Hour, reaction terminates rear slurry and naturally cools to room temperature, through washing, filtering, dry, obtains final phosphoric acid ferrimanganic (one, band
The crystallization water) product, its chemical formula is Mn0.8Fe0.2PO4·H2O。
Embodiment 6
The Mn nitrate solution (0.3984mol) that 100mL concentration is 47.62% is weighed, and adds 100 water and is well mixed,
80mL mass concentrations are added as 25% ammoniacal liquor (1.035mol) by peristaltic pump while stirring, adjustment system pH to 8.12,
Continue stirring 10 minutes after end to be added, 65mL is then added with 80r/min charging rate by peristaltic pump while stirring
Mass concentration is 30% hydrogen peroxide (0.5876mol), and reaction to be oxidized continues stirring 40 minutes after terminating, then by 50mL
The nine water iron nitrate solutions (0.0996mol) that concentration is 1.99mol/L add system, are well mixed stirring 30 minutes, then will
Reactor is heated to 165 DEG C, then adds the phosphoric acid (0.6557mol) that 45mL mass concentrations are 85%, reacts 6 hours, reaction
Slurry naturally cools to room temperature after end, through washing, filtering, dry, obtains final phosphoric acid ferrimanganic (one crystallization water of band) production
Product, its chemical formula are Mn0.8Fe0.2PO4·H2O。
Embodiment 7
75.00g sulfuric acid monohydrates Asia manganese (0.4437mol) and 123.37g ferrous sulfate heptahydrates (0.4437mol) are weighed, it is molten
Solution adds the ammoniacal liquor (1.4882mol) that 115mL concentration is 25% by peristaltic pump while stirring, adjusts system in 500mL water
PH value continues stirring 10 minutes, then while stirring by peristaltic pump with 50r/min charging speed to 7.52 after end to be added
Degree adds the hydrogen peroxide (0.9304mol) that 95mL mass concentrations are 30%, and reaction to be oxidized continues stirring 30 minutes after terminating,
Then reactor is heated to 85 DEG C, then adds the phosphoric acid (1.0929mol) that 75mL mass concentrations are 85%, react 8 hours,
Reaction terminates rear slurry and naturally cools to room temperature, through washing, filtering, dry, obtains (one crystallization of band of final phosphoric acid ferrimanganic
Water) product, its chemical formula is Mn0.5Fe0.5PO4·H2O。
Embodiment 8
The Mn nitrate solution (0.3984mol) that 100mL concentration is 47.62% is weighed, and adds 100 water and is well mixed,
80mL mass concentrations are added as 25% ammoniacal liquor (1.035mol) by peristaltic pump while stirring, adjustment system pH to 8.12,
Continue stirring 10 minutes after end to be added, 65mL is then added with 80r/min charging rate by peristaltic pump while stirring
Mass concentration is 30% hydrogen peroxide (0.5876mol), and reaction to be oxidized continues stirring 40 minutes after terminating, then by 50mL
The nine water iron nitrate solutions (0.0996mol) that concentration is 1.99mol/L add system, are well mixed stirring 30 minutes, then will
Reactor is heated to 165 DEG C, then adds the phosphoric acid (0.6557mol) that 45mL mass concentrations are 85%, reacts 6 hours, reaction
Slurry naturally cools to room temperature after end, through washing, filtering, dry, obtains final phosphoric acid ferrimanganic (one crystallization water of band) production
Product, its chemical formula are Mn0.8Fe0.2PO4·H2O.Ferric phosphate manganese product prebake in 550 DEG C of air that 100g has been prepared
Burn 3 hours, naturally cool to room temperature, it is standby to treat.Li/ (Mn+Fe)=1.10 is weighed in molar ratio for the preparation of lithium ferric manganese phosphate
Raw material, the burned phosphoric acid ferrimanganic of lithium carbonate, prebake, 9.38g starch are added the sand mill containing 1600mL ethanol and carried out successively
Grinding 4 hours, after raw meal particle size is 200~300nm, slurry is taken out, is dried, is crushed.Under nitrogen protection, after will be broken
Material is placed in tube furnace and sintered 8 hours, 680 DEG C of sintering temperature, takes out material after tube furnace Temperature fall, obtains ferric phosphate
Manganese lithium product Li1.1Mn0.8Fe0.2PO4。
Above content is only that affiliated those skilled in the art are to being retouched to examples of the invention and explanation
Various modifications may be made or supplement for the specific embodiment stated, and design without departing from the present invention or surmounts the claims and is defined
Scope, protection scope of the present invention all should be belonged to.
Claims (9)
1. a kind of preparation method of phosphoric acid ferrimanganic, it is characterised in that it is as follows that the method comprising the steps of：
1) salt-mixture of manganous salt and divalent iron salt is added in reactor, adds water, being stirred at room temperature is completely dissolved it,
It is configured to the aqueous solution of manganous salt that concentration is respectively 0.2~4mol/L and divalent iron salt；
2) the pH regulators that have prepared are added by peristaltic pump while stirring into reactor, adjust the pH value of reaction system to
7.5~12.0, continue stirring after terminating 10~20 minutes；
3) oxidant is added with 30~100r/min charging rate by peristaltic pump into reactor, continues stirring 20 after terminating
~60 minutes；
4) after temperature reaches 60~165 DEG C in question response kettle, soluble sources solution is added with peristaltic pump, is reacted 2~8 hours,
Reaction terminates rear phosphoric acid ferrimanganic slurry and naturally cools to room temperature, through washing, filtering, dry, obtains finished product MnxFe1-xPO4·
yH2O。
2. preparation method as claimed in claim 1, it is characterised in that：
1) manganous salt described in is manganese sulfate, the one or more in Mn nitrate, protochloride manganese, acetic acid Asia manganese；
2) divalent iron salt described in is ferrous sulfate, the one or more in ferrous nitrate, frerrous chloride；
3) the pH regulators described in are sodium hydroxide, the one or more in ammoniacal liquor, sodium acetate, ammonium acetate；
4) oxidant described in is sodium peroxide, one or more in hydrogen peroxide, ozone, wherein oxidant and manganese and mole of iron
Than i.e. oxidant/(Mn+Fe)=1~4；
5) phosphorus source described in is phosphoric acid, the one or more in sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, ammonium phosphate, phosphorus source and manganese
Mol ratio with iron is P/ (Mn+Fe)=1.1~2；
6) it is Mn/Fe=1~4 by the raw materials components mole ratio for adjusting manganese salt and molysite, the phosphorus of different Mn/Fe mol ratios can be obtained
Sour ferrimanganic MnxFe1‐xPO4·yH2O products, 0.5≤x≤0.8, y values are 0 or 1.
3. preparation method as claimed in claim 1, it is characterised in that：
1) manganous salt is added in reactor, adds water, being stirred at room temperature is completely dissolved it, be configured to concentration for 0.2~
The aqueous solution of 4mol/L manganous salt；
2) the pH regulators that have prepared are added by peristaltic pump while stirring into reactor, adjust the pH value of reaction system to
7.5~12.0, continue stirring after terminating 10~20 minutes；
3) oxidant is added with 30~100r/min charging rate by peristaltic pump into reactor, continues stirring 20 after terminating
~60 minutes；
4) ferric salt solution prepared is added by peristaltic pump into reactor, continues stirring 30 minutes after terminating；Three
Valency iron salt solutions concentration is 0.2~4mol/L；
5) after temperature reaches 60~165 DEG C in question response kettle, a certain amount of soluble sources solution, reaction 2 are added with peristaltic pump
~8 hours, reaction terminated rear phosphoric acid ferrimanganic slurry and naturally cools to room temperature, through washing, filtering, dry, obtained finished product
MnxFe1-xPO4·yH2O。
4. preparation method as claimed in claim 3, it is characterised in that：
1) manganous salt described in is manganese sulfate, the one or more in Mn nitrate, protochloride manganese, acetic acid Asia manganese；
2) the pH regulators described in are sodium hydroxide, the one or more in ammoniacal liquor, sodium acetate, ammonium acetate；
3) oxidant described in is sodium peroxide, one or more in hydrogen peroxide, ozone, wherein oxidant and manganese and mole of iron
Than oxidant/(Mn+Fe)=1~4；
4) trivalent iron salt described in is ferric sulfate, the one or more in ferric nitrate, iron chloride；
5) phosphorus source described in is phosphoric acid, the one or more in sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, ammonium phosphate, phosphorus source and manganese
Mol ratio with iron is P/ (Mn+Fe)=1.1~2；
6) it is Mn/Fe=1~4 by the raw materials components mole ratio for adjusting manganese salt and molysite, the phosphorus of different Mn/Fe mol ratios can be obtained
Sour ferrimanganic MnxFe1‐xPO4·yH2O products, 0.5≤x≤0.8, y values are 0 or 1.
5. ferric phosphate manganese product prepared by the method according to any one of Claims 1 to 4.
6. a kind of lithium ferric manganese phosphate, phosphoric acid ferrimanganic and lithium compound made of by any one of Claims 1 to 4 methods described
Synthesis forms.
7. lithium ferric manganese phosphate as claimed in claim 6, it is characterised in that described lithium compound be lithium carbonate, lithium hydroxide,
One or more in lithium acetate.
8. a kind of cell positive material, the cell positive material is used through discharge and recharge is repeated in battery electrode two
The positive electrode of primary cell, based on the lithium ferric manganese phosphate described in claim 6.
9. a kind of secondary cell, it is made with the cell positive material described in claim 8.
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