CN105810943B - A kind of method that zinc doping LiFePO4 is prepared using phosphatization slag - Google Patents
A kind of method that zinc doping LiFePO4 is prepared using phosphatization slag Download PDFInfo
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- CN105810943B CN105810943B CN201610318093.1A CN201610318093A CN105810943B CN 105810943 B CN105810943 B CN 105810943B CN 201610318093 A CN201610318093 A CN 201610318093A CN 105810943 B CN105810943 B CN 105810943B
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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
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- 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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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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- 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
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Abstract
The invention belongs to technical field of new energy material preparation, specially a kind of method that zinc doping LiFePO4 is prepared using phosphatization slag.The inventive method specifically includes following steps:First pass through acid wash and purified from phosphatization slag and obtain the ferric phosphate containing trace zinc, then mix lithium source, carbon source by a certain percentage with the ferric phosphate containing trace zinc, ball milling, drying are calcined in protective atmosphere, and zinc doping LiFePO4 is obtained after cooling.Method proposed by the present invention realizes the recycling to ferric phosphate principal component contained by phosphatization slag, and specific capacity height, the zinc doping lithium iron phosphate positive material of good cycle of acquisition have important actual application value.
Description
Technical field
The present invention relates to technical field of new energy material preparation, specifically, it is related to and a kind of prepare zinc using phosphatization slag and mix
The method of miscellaneous LiFePO4.
Background technology
Phosphatization is one of important preprocessing mode before coated metal, in chemical industry, metallurgy, automobile, space flight and aviation, household electric
The fields such as device suffer from being widely applied.Phosphatization slag is caused solid waste in parkerizing process, and its main component is phosphoric acid
Iron and trbasic zinc phosphate, also, if mishandling, serious dirt will certainly be caused to environment containing a small amount of nickel, cadmium, manganese plasma in addition
Dye.Therefore, study by the technology that phosphatization slag is turned waste into wealth to improve resource utilization, reduce environmental pollution it is significant.
The LiFePO4 of olivine structural has higher theoretical capacity(170mAh/g), good cyclical stability, can
The security leaned on and it is cheap the advantages that, it has also become the preferred positive electrode of power lithium-ion battery.Ferric phosphate is to prepare phosphorus
One of primary raw material of sour iron lithium, the LiFePO4 of industrialized production is made using the ferric phosphate chemical reagent of high cost at present
Raw material.Utilize inductively coupled plasma(ICP)Test analysis draws the content of ferric phosphate in phosphatization slag 75% ~ 80%, if energy
Ferric phosphate is extracted as the raw material for preparing LiFePO4 from phosphatization slag, can not only be mitigated dirty to caused by environment
Dye, and the production cost of LiFePO4 can be significantly reduced, realize reusing for resource.
Chinese patent CN103832990A discloses a kind of method that ferric phosphate is extracted in waste residue from phosphatization.First use concentrated hydrochloric acid
Phosphatization slag is dissolved, then adds sodium hydroxide, the foreign ion in solution is removed using precipitation reaction.This method is present
Production cost is higher, and the problems such as substantial amounts of acidic and alkaline waste water can be produced.Chinese patent CN102593450A is using oxidation and acid
The method washed is purified to phosphatization slag, and the ferric phosphate of multi-element doping has then been prepared using the phosphatization slag after purification as raw material
Lithium.But there is technological process complexity in above method, purify the shortcomings of obtained ferric phosphate purity is not high.
The content of the invention
To solve the deficiencies in the prior art, zinc doping phosphoric acid is prepared using phosphatization slag it is an object of the invention to provide one kind
The method of iron lithium.Its simple to operate, economy, secondary pollution are small.
Technical scheme is specifically described as follows.
The present invention provides a kind of method that zinc doping LiFePO4 is prepared using phosphatization slag, comprises the following steps that:
(1)The floating object of suspension surface after phosphatization slag is uniformly mixed with distilled water, is stood, removes, then thereto
The first inorganic acid is added, 1 ~ 24h of synthesis under normal pressure at a temperature of 30 ~ 150 DEG C, is filtered after cooling, obtains filter cake;
(2)By step(1)In filter cake mixed with distilled water, add the second inorganic acid, 80 ~ 250 DEG C of temperature in reactor
Under degree, under 1 ~ 4MPa pressure, 1 ~ 24h of reaction under high pressure, filter, the drying of gained filter cake, grinding, obtain the phosphoric acid iron powder containing zinc
End;
(3)Lithium source and carbon source are added into the phosphoric acid iron powder containing zinc, using absolute ethyl alcohol as medium, ball milling mixing, is dried
It is dry;
(4)By step(3)Gained sample under protective atmosphere in tube furnace at a temperature of 50 ~ 1000 DEG C constant temperature processing 1 ~
After 24h, cooling, zinc doping lithium iron phosphate positive material i.e. is obtained to sinter pulverization process.
In the present invention, the first inorganic acid, the second inorganic acid independence in concentrated phosphoric acid, sulfuric acid, nitric acid or hydrochloric acid
Any one or more.
Above-mentioned steps(1)In, the mass ratio of first inorganic acid and phosphatization slag is 0.5:40~6:40, preferably 0.8:
40~5:40, more preferably 0.9:40~4.5:40.
Above-mentioned steps(1)In, the reaction temperature is preferably 50 ~ 120 DEG C, more preferably 60 ~ 100 DEG C;The reaction
Time is preferably 5 ~ 18h, more preferably 6 ~ 12h.
Above-mentioned steps(2)In, the mass ratio of the second inorganic acid and phosphatization slag is 0.2:40~4:40, preferably 0.3:40~
3.5:40, more preferably 0.5:40~3:40.
Above-mentioned steps(2)In, reaction temperature is preferably 90 ~ 200 DEG C, more preferably 100 ~ 180 DEG C;Reaction time is preferred
For 4 ~ 19h, more preferably 5 ~ 16h.
Above-mentioned steps(3)In, the ferric phosphate containing zinc is 1 with lithium source, the mol ratio of carbon source:(0.90~1.1):(0.02~
2.5), preferably 1:(0.93~1.08):(0.04~2.2), more preferably 1:(0.95~1.04):(0.05~2.1).
Above-mentioned steps(3)In, lithium source is the one or more in lithium nitrate, lithium carbonate, lithium hydroxide or lithium acetate;Carbon source
For the one or more in glucose, citric acid, sucrose or ascorbic acid.
Above-mentioned steps(4)In, protective atmosphere is a kind of in argon gas, nitrogen or helium, it is preferred that under nitrogen atmosphere
Carry out.
Above-mentioned steps(4)In, reaction temperature is preferably 550 ~ 900 DEG C, more preferably 600 ~ 850 DEG C;Reaction time is excellent
Elect 5 ~ 20h, more preferably 7 ~ 16h as.
Zinc doping LiFePO4, which is prepared, in the above-mentioned preparation method of the present invention can be used as anode material of lithium battery.
In the present invention, by the amount for controlling the first inorganic acid, it is ensured that what the ferric phosphate in suspension was not dissolved
In the case of, and make the overwhelming majority dissolving of the materials such as trbasic zinc phosphate therein, nickel phosphate, cadmium phosphate, in ionic condition, then by taking out
Filter, remove the foreign ion such as most zinc, nickel, cadmium in phosphatization slag.By the amount for controlling the second inorganic acid, it is ensured that outstanding
In the case that ferric phosphate in supernatant liquid is not dissolved, and make the materials such as the trbasic zinc phosphate, nickel phosphate, cadmium phosphate that wherein remain on a small quantity molten
Solution, in ionic condition, then by filtering, the foreign ions such as the zinc remained on a small quantity in phosphatization slag, nickel, cadmium are removed, obtain purity
Higher ferric phosphate.
Material crystal structure is tested using German Bruker D8 ADVANCE type X-ray diffractometers in the present invention, is adopted
With Cu-K α radiation sources, tube voltage 40KV, tube current 40mA, scanning range is 10o ~ 80o.
The electrical property of lithium iron phosphate positive material is carried out using Wuhan LAND CT-2001 battery test systems in the present invention
Test, the voltage range of button cell test is 2.5 ~ 4.2V.
Battery initial charge specific capacity of the present invention=(Initial charge capacity/active material quality under 0.1C electric currents)×
1000。
Battery first discharge specific capacity of the present invention=(Discharge capacity/active material quality first under 0.1C electric currents)×
1000。
Battery of the present invention first coulombic efficiency=(Discharge capacity/initial charge capacity first)×100.
The present invention has the advantages that:This method purifies obtained iron phosphate grains better crystallinity degree, and purity is higher,
ICP test results show phosphoric acid iron content more than 98%;The active ingredient in phosphatization slag can be made full use of, is saved substantial amounts of
Phosphorus, iron resource;A kind of practicable phosphatization Slag treatment method is provided, the phosphatization slag that annual tons up to a million can be made discarded is recovered
Recycle, reduce the destruction to environment and the ecosystem;Zinc doping LiFePO4 prepared by this method is applied to lithium electricity industry, gathers around
There is huge market capacity, abundant economic benefit can be brought.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates for the phosphoric acid iron sample that the purification of embodiment 1 obtains.
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of zinc doping LiFePO4 prepared by embodiment 1.
Fig. 3 is ESEM (SEM) figure of zinc doping LiFePO4 prepared by embodiment 1.
Fig. 4 is the first charge-discharge curve map of zinc doping lithium iron phosphate positive material prepared by embodiment 1.
Fig. 5 is the cycle performance curve map of zinc doping lithium iron phosphate positive material prepared by embodiment 1.
Embodiment
Embodiments of the invention are described in further detail below in conjunction with the accompanying drawings, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1
Take 80g phosphatization slags to be dissolved in 60g distilled water, stir, remove the floating object of suspension surface, it is dense then to add 8.5g
Phosphoric acid (concentration 85wt%), it is well mixed after synthesis under normal pressure 10h at 70 DEG C, filters, gained filter cake mixes with distilled water again
Close, add 4.2g concentrated phosphoric acids (concentration 85wt%) thereto, react 12h in 160 DEG C of reactor mesohighs, filter, filter cake is washed
Wash to neutrality and dried after at 90 DEG C, 200 mesh sieves are crossed after grinding, that is, obtain the phosphoric acid iron powder containing trace zinc.ICP test knots
Fruit shows that the phosphoric acid iron content in LiFePO4 sample obtained by the present embodiment is 99.1%.
30g phosphoric acid iron powders are taken, while add 7.2g lithium carbonates, 5.6g glucose, using absolute ethyl alcohol as medium,
Ball milling mixing 5h under 500r/min rotating speed, then to dry at 70 DEG C, gained sample is fitted into crucible, under nitrogen atmosphere, in
Constant temperature 10h in 750 DEG C of tube furnace, zinc doping lithium iron phosphate positive material is obtained after cooling, is surveyed after being fabricated to button cell
Try its chemical property.
The X-ray diffraction of phosphoric acid iron sample obtained by the present embodiment(XRD) collection of illustrative plates is as shown in Figure 1.Sample collection of illustrative plates and diffraction number
According to ferric phosphate(Card number:29-0715)Standard spectrum and diffraction data are closely similar, and the ferric phosphate purity for illustrating to obtain is higher.
The X-ray diffraction of LiFePO4 sample obtained by the present embodiment(XRD) collection of illustrative plates is as shown in Figure 2.Sample collection of illustrative plates and diffraction
Data and LiFePO4(Card number:81-1173)Standard spectrum and diffraction data contrast illustrate micro almost without obvious impurities phase
Zinc have been introduced into the lattice of LiFePO4 among form zinc doping LiFePO4.
The ESEM of LiFePO4 sample obtained by the present embodiment(SEM)Figure is as shown in Figure 3.As seen from the figure, the zinc of preparation
Doped iron lithium phosphate sample particle is uniform in size, good dispersion.
The first charge-discharge curve of lithium iron phosphate positive material is as shown in Figure 4 obtained by the present embodiment.Under 0.1c electric currents, its
Initial charge specific capacity is 154.75mAhg-1, first discharge specific capacity 144.74mAhg-1, first coulombic efficiency be
93.53%。
The cycle performance curve of lithium iron phosphate positive material is as shown in Figure 5 obtained by the present embodiment.Under 1c electric currents, fill for 20 times
After discharge cycles, its charge specific capacity is 129.87mAhg-1, capability retention 94.55%.
Embodiment 2
Take 80g phosphatization slags to be dissolved in 60g distilled water, stir, remove the floating object of suspension surface, it is dense then to add 8.9g
Sulfuric acid (concentration 98wt%), it is well mixed after synthesis under normal pressure 20h at 30 DEG C, filters, gained filter cake mixes with distilled water again
Close, add 5.5g watery hydrochloric acid (concentration 8wt%) thereto, react 5h in 220 DEG C of reactor mesohighs, filter, Washing of Filter Cake
Dried to neutrality after at 90 DEG C, 200 mesh sieves are crossed after grinding, that is, obtain the phosphoric acid iron powder containing trace zinc.ICP test results
Show the phosphoric acid iron content in LiFePO4 sample obtained by the present embodiment 98.5%.
30g phosphoric acid iron powders are taken, while add 7.2g lithium carbonates, 5.6g sucrose, using absolute ethyl alcohol as medium, in 500r/
Ball milling mixing 5h under min rotating speed, then dry at 70 DEG C, gained sample is fitted into crucible, under nitrogen atmosphere, in 1000 DEG C
Tube furnace in constant temperature 4h, obtain zinc doping lithium iron phosphate positive material after cooling, be fabricated to after button cell and test its electricity
Chemical property.Its initial charge specific capacity is 157.79mAhg under 0.1c electric currents-1, first discharge specific capacity is
149.59mAh·g-1, coulombic efficiency is 94.8% first.After lower 20 charge and discharge cycles of 1c electric currents, charge specific capacity is
149.77mAh·g-1, capability retention 94.92%.
Embodiment 3
Take 80g phosphatization slags to be dissolved in 60g distilled water, stir, remove the floating object of suspension surface, it is dense then to add 7.1g
Nitric acid (concentration 68wt%), it is well mixed after synthesis under normal pressure 2h at 150 DEG C, filters, gained filter cake mixes with distilled water again
Close, add 3.5g concentrated phosphoric acids (concentration 85wt%) thereto, react 22h in 90 DEG C of reactor mesohighs, filter, filter cake is washed
Wash to neutrality and dried after at 90 DEG C, 200 mesh sieves are crossed after grinding, that is, obtain the phosphoric acid iron powder containing trace zinc.ICP test knots
Fruit shows phosphoric acid iron content in LiFePO4 sample obtained by the present embodiment 98.3%.
30g phosphoric acid iron powders are taken, while add 4.6g lithium hydroxides, 5.6g ascorbic acid, using absolute ethyl alcohol as medium,
Ball milling mixing 5h under 500r/min rotating speed, then to dry at 70 DEG C, gained sample is fitted into crucible, under nitrogen atmosphere, in
Constant temperature 18h in 600 DEG C of tube furnace, zinc doping lithium iron phosphate positive material is obtained after cooling, is surveyed after being fabricated to button cell
Try its chemical property.Its initial charge specific capacity is 146.84mAhg under 0.1c electric currents-1, first discharge specific capacity is
136.05mAh·g-1, coulombic efficiency is 92.65% first.After lower 20 charge and discharge cycles of 1c electric currents, charge specific capacity is
119.65mAh·g-1, capability retention 92.43%.
Embodiment 4
Take 80g phosphatization slags to be dissolved in 60g distilled water, stir, remove the floating object of suspension surface, it is dense then to add 10g
Phosphoric acid (concentration 85wt%), it is well mixed after synthesis under normal pressure 8h at 90 DEG C, filters, gained filter cake mixes with distilled water again,
6.5g dust technologies (concentration 15wt%) are added thereto, are reacted 15h in 140 DEG C of reactor mesohighs, are filtered, Washing of Filter Cake
Dried to neutrality after at 90 DEG C, 200 mesh sieves are crossed after grinding, that is, obtain the phosphoric acid iron powder containing trace zinc.ICP test results
Show the phosphoric acid iron content in phosphoric acid iron sample obtained by the present embodiment more than 99.2%.
30g phosphoric acid iron powders are taken, while add 7.2g lithium carbonates, 5.6g glucose, using absolute ethyl alcohol as medium,
Ball milling mixing 5h under 500r/min rotating speed, then to dry at 70 DEG C, gained sample is fitted into crucible, under nitrogen atmosphere, in
Constant temperature 7h in 900 DEG C of tube furnace, zinc doping lithium iron phosphate positive material is obtained after cooling, is tested after being fabricated to button cell
Its chemical property.Its initial charge specific capacity is 150.32mAhg under 0.1c electric currents-1, first discharge specific capacity is
139.53mAh·g-1, coulombic efficiency is 92.82% first.After lower 20 charge and discharge cycles of 1c electric currents, charge specific capacity is
139.83mAh·g-1, capability retention 93.02%.
Embodiment 5
Take 80g phosphatization slags to be dissolved in 60g distilled water, stir, remove the floating object of suspension surface, it is dense then to add 7.8g
Sulfuric acid (concentration 98wt%), it is well mixed after synthesis under normal pressure 6h at 120 DEG C, filters, gained filter cake mixes with distilled water again
Close, add 4.5g concentrated nitric acids (concentration 85wt%) thereto, react 10h in 180 DEG C of reactor mesohighs, filter, filter cake is washed
Wash to neutrality and dried after at 90 DEG C, 200 mesh sieves are crossed after grinding, that is, obtain the phosphoric acid iron powder containing trace zinc.ICP test knots
Fruit shows phosphoric acid iron content in phosphoric acid iron sample obtained by the present embodiment 98.7%.
30g phosphoric acid iron powders are taken, while add 4.6g lithium hydroxides, 5.6g sucrose, using absolute ethyl alcohol as medium,
Ball milling mixing 5h under 500r/min rotating speed, then to dry at 70 DEG C, gained sample is fitted into crucible, under nitrogen atmosphere, in
Constant temperature 9h in 850 DEG C of tube furnace, zinc doping lithium iron phosphate positive material is obtained after cooling, is tested after being fabricated to button cell
Its chemical property.Its initial charge specific capacity is 154.69mAhg under 0.1c electric currents-1, first discharge specific capacity is
138.09mAh·g-1, coulombic efficiency is 89.27% first.After lower 20 charge and discharge cycles of 1c electric currents, charge specific capacity is
125.11mAh·g-1, capability retention 91.12%.
Comparative example
Take 30g phosphoric acid iron powders(AR, Chemical Reagent Co., Ltd., Sinopharm Group), while add 7.2g lithium carbonates, 5.6g
Glucose, using absolute ethyl alcohol as medium, the ball milling mixing 5h under 500r/min rotating speed, then dry at 70 DEG C, gained sample
It is fitted into crucible, under nitrogen atmosphere, the constant temperature 10h in 750 DEG C of tube furnace, iron phosphate lithium positive pole material is obtained after cooling
Material, its chemical property is tested after being fabricated to button cell.Its initial charge specific capacity is 149.82mAhg under 0.1c electric currents-1, first discharge specific capacity 134.63mAhg-1, coulombic efficiency is 89.86% first.Lower 20 charge and discharge cycles of 1c electric currents
Afterwards, charge specific capacity 121.32mAhg-1, capability retention 91.61%.
Table 1 is the charge-discharge performance related data of embodiment and comparative example.
The embodiment of table 1 and comparative example charge-discharge test data
It is uniform that test result more than can be seen that the zinc doping lithium iron phosphate positive material particle for preparing of the present invention,
Good dispersion;With higher coulombic efficiency first and preferable cycle performance;In addition, cyclic voltammetry result shows, this
Zinc doping lithium iron phosphate positive material prepared by invention has good invertibity.
Claims (5)
- A kind of 1. method that zinc doping LiFePO4 is prepared using phosphatization slag, it is characterised in that comprise the following steps that:(1)The floating object of suspension surface after phosphatization slag is uniformly mixed with distilled water, is stood, removed, is then added thereto First inorganic acid, 1 ~ 24h of synthesis under normal pressure at a temperature of 30 ~ 150 DEG C, filters after cooling, obtains filter cake;(2)By step(1)In filter cake mixed with distilled water, add the second inorganic acid, in reactor at a temperature of 80 ~ 250 DEG C, Under 1 ~ 4MPa pressure, 1 ~ 24h of reaction under high pressure, filter, the drying of gained filter cake, grinding, obtain the phosphoric acid iron powder containing zinc;(3)Lithium source and carbon source are added into the phosphoric acid iron powder containing zinc, using absolute ethyl alcohol as medium, ball milling mixing, drying;(4)By step(3)Gained sample after constant temperature processing, cooling, crushes under protective atmosphere in tube furnace to sinter Processing obtains zinc doping LiFePO 4 material;Wherein:Reaction temperature is 550 ~ 900 DEG C;Reaction time is 5 ~ 20h;Wherein:Any one in concentrated phosphoric acid, the concentrated sulfuric acid, concentrated nitric acid or concentrated hydrochloric acid of first inorganic acid, the second inorganic acid independence It is or a variety of;Step(1)In, the mass ratio of the first inorganic acid and phosphatization slag is 0.5:40~6:40, reaction temperature is 50 ~ 120 DEG C;Reaction Time is 5 ~ 18h;Step(2)In, the mass ratio of the second inorganic acid and phosphatization slag is 0.2:40~4:40;Reaction temperature is 90 ~ 200 DEG C, reaction Time is 4 ~ 19h.
- 2. the method as described in claim 1, it is characterised in that:Step(3)In, the ferric phosphate containing zinc and lithium source, carbon source Mol ratio is 1:(0.90~1.1):(0.02~2.5).
- 3. the method as described in claim 1, it is characterised in that:Step(3)In, lithium source is selected from lithium nitrate, lithium carbonate, hydroxide One or more in lithium or lithium acetate;One or more of the carbon source in glucose, citric acid, sucrose or ascorbic acid.
- 4. the method as described in claim 1, it is characterised in that:Step(4)In, the protective atmosphere be argon gas, nitrogen or It is a kind of in helium.
- 5. the method as described in one of claim 1-4, it is characterised in that the zinc doping LiFePO4 being prepared is used as lithium electricity Pond positive electrode.
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CN111807342A (en) * | 2020-08-10 | 2020-10-23 | 上海第二工业大学 | Method for purifying and preparing submicron-grade iron phosphate from phosphated slag |
CN112678794A (en) * | 2021-01-29 | 2021-04-20 | 刘娱雪 | Method for preparing multi-element doped lithium iron phosphate from phosphorized slag |
CN115010107A (en) * | 2022-06-09 | 2022-09-06 | 湖北万润新能源科技股份有限公司 | Method for preparing lithium iron manganese phosphate cathode material from phosphorized slag |
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CN103832990A (en) * | 2012-11-27 | 2014-06-04 | 重庆能源职业学院 | Method for extracting ferric phosphate from phosphorized waste residues |
CN105236375A (en) * | 2015-09-17 | 2016-01-13 | 上海第二工业大学 | Method for preparing hydrated hydroxyl ferric phosphates by utilizing waste phosphatization slag for extraction |
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