CN103367747A - Method for preparing lithium iron phosphate battery material from ferrophosphorus - Google Patents
Method for preparing lithium iron phosphate battery material from ferrophosphorus Download PDFInfo
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- CN103367747A CN103367747A CN2013103075560A CN201310307556A CN103367747A CN 103367747 A CN103367747 A CN 103367747A CN 2013103075560 A CN2013103075560 A CN 2013103075560A CN 201310307556 A CN201310307556 A CN 201310307556A CN 103367747 A CN103367747 A CN 103367747A
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- lithium
- ferrophosphorus
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- carbon
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Abstract
The invention discloses a method for preparing a lithium iron phosphate battery material from ferrophosphorus. The method comprises the processes: with a yellow phosphorus by-product ferrophosphorus as raw material, supplementing a certain amount of phosphate element, lithium element, carbon element to produce the lithium iron phosphate battery electrode material. The method is characterized by: firstly crushing the ferrophosphorus to granules with the particle size of 3 mm or less, putting into a stirring pulverizer, grinding until the particle size is less than 100 mesh, sending into a rotary furnace for air oxidation and roasting, cooling, blending, stirring and grinding again for 30 minutes to 2 hours; sending into a calcining furnace for a sintered reaction, after finishing reaction, cooling the materials, then stirring and grinding again for 1 to 3 hours, carrying out analytical test, packaging, to obtain the lithium iron phosphate battery electrode material. The method has the production cost which is the lowest at home and abroad currently, is in all solid state production, requires no atmosphere protection, and has simple equipment; and the product has high tap density, good quality stability and high specific capacity, has the initial capacity of up to 154.5 mAh.g<-1> when the discharge rate is 0.2 C, and still maintains more than 90% of the initial capacity after 100 times cycles.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of manufacturing technique method of lithium iron phosphate battery positive material.
Background technology
LiFePO4 (LiFePO
4), because the advantage such as cheap, good stability, nontoxic, good cycle and security performance be good is considered to the most promising positive electrode of lithium ion battery of future generation.The application of lithium iron phosphate positive material on lithium ion battery, poor stability, the safeguard measure that can effectively break existing lithium ion battery be complicated, be difficult to maximize and the factor such as high cost to the restriction of the industrial chains such as large power supply, electric automobile.
The method of existing production lithium iron phosphate positive material is as follows both at home and abroad:
1. high temperature solid-state method: with ferrous salt (ferrous oxalate, ferric acetate, ferrous phosphate etc.), phosphate (diammonium hydrogen phosphate, ammonium dihydrogen phosphate), lithium salts (lithium carbonate, lithium hydroxide, lithium acetate and lithium phosphate etc.) is raw material, presses LiFePO
4The atomic ratio of molecular formula is prepared burden, and a step, two steps or the heating of three steps can get LiFePO after the cooling in protective atmosphere (mist of nitrogen, argon gas or they and hydrogen)
4Powder body material.The method mainly exists calcination process to need Buchholz protection, has the ammonia nitrogen compound exhaust air to produce, and the product tap density is poor, the deficiency that electrical efficiency is poor.
2. hydrothermal synthesis method: the village is large high with LiOH, FeSO
4And H
3PO
4Be dissolved in deionized water, stir it is fully reacted after, put into closed reactor, obtain behind 150 ℃ of lower heating 15h that purity is high, the nanometer LiFePO of advantages of good crystallization
4, its granularity is 800nm, the LiFePO after 550 ℃ of lower polypropylene pyrolysis carbon coat processing
4/ C composite material.Mainly there is the dislocation that usually exists iron in the product structure of preparation in the method, has generated metastable FePO4, has affected chemistry and the chemical property of product; Have also simultaneously that particle diameter is inhomogeneous, phase is impure, equipment investment large (high temperature high voltage resistant reactor to manufacture and design difficulty large, cost is also high), technique is complicated, product cost is high shortcoming; Be only limited to the preparation of a small amount of powder, the deficiency that the difficulty of suitability for industrialized production is larger.
3. the precipitation method: K.S.Park etc. are with (NH
4)
2Fe (SO
4)
26H
2O and H
3PO
4The aqueous solution join in the aqueous solution of LiOH, flow down at nitrogen and form green precipitate after stirring 10min, will mix with high surface area carbon black after the washing of precipitate drying, under nitrogen protection, synthesized end product LiFePO in 600 ℃ after calcining 5h again
4/ C composite material.The method exists the different material requirement to have similar hydrolysis or deposition condition and has limited the range of choice of raw material, has affected its practical application; And having increased the cost of product and the complexity of production technology, process produces a large amount of waste water, waste gas to be needed to process.
The problems such as at present, LiFePO4 also is not applied on a large scale, and is relatively poor mainly due to the high rate performance of technical elements, that homogeneity of product is good not, cryogenic property is undesirable,, the restriction of foreign patent and production cost are crossed high impact.The industrialization of LiFePO 4 material is in the starting stage basically, and LiFePO4 also needs to continue deeply as research and the industrialization process of the positive electrode of electrokinetic cell.
The purpose of this bright invention is to put forth effort to solve the Fe that exists in the current lithium ion battery development
2+Easily be oxidized to Fe
3+, irreversible capacity loss, the quality stability of guaranteeing different production batch, the tap density that improves ferric phosphate lithium cell that cause of the serious reunion in the playback electric process, the problem such as electrical efficiency that improves, further simplify LiFePO4 production technology, adapt to industrialization, in enormous quantities, serialization and reduce production costs to greatest extent, huge progradation will be arranged the application of lithium-ion-power cell.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method of ferrophosphorus preparing phosphoric acid lithium iron battery electrode material.The purpose of this bright invention is: put forth effort to solve the Fe that exists in the current lithium ion battery development
2+Easily be oxidized to Fe
3+, irreversible capacity loss, the quality stability of guaranteeing different production batch, the tap density that improves the ferric phosphate lithium cell electrode material that cause of the serious reunion in the playback electric process, improve electrical efficiency, simplify LiFePO4 production technology, adapt to industrialization, the demand that in enormous quantities, serialization is produced and the problem such as reduce production costs to greatest extent.
The technical solution adopted in the present invention is: take yellow phosphorus by-product ferrophosphorus as raw material, replenish the process of a certain amount of phosphorus, lithium, carbon production ferric phosphate lithium cell material, it is characterized in that: ferrophosphorus is just broken granular to 3mm, enter the stirring flour mill, be ground to particle diameter less than 100 orders, send into rotary furnace and carry out the air oxidation roasting, temperature of charge in the control stove: 600～1000 ℃, roasting time: 1.5～4 hours, under stirring and the state of oxidation, make the oxygen uptake of ferrophosphorus powder, change into the mixture of ferrous phosphate, iron oxide and ferric phosphate.Before oxidizing roasting, the ferrophosphorus powder of the ferrophosphorus of not roasting and roasting can be carried out oxidizing roasting after by 1: 0.3～1 volume or weight ratio batching mixing, can improve the oxygen uptake roasting efficient minimizing roasting time of ferrophosphorus powder.。Relevant chemical equation: a.4Fe
2P+8O
2→ 2Fe
3(PO4)
2+ Fe
2B.4Fe
2P+11O
2→ 4FePO
4+ 2Fe
2O
3C.2Fe
2O
3+ 4H
3PO
4→ 4FePO
4+ 6H
2O; After the oxidizing roasting fully, material is cooled to about 100 ℃, according to (iron: phosphorus=1: 0.555～0.62; Iron: lithium=1: 0.124～0.18; All by the element wt ratio) element ratio in the roasting material, add P elements and elemental lithium; (adding P elements can be with a kind of or mixture in the phosphoric acid of food-grade, ammonium phosphate, the lithium dihydrogen phosphate, adds elemental lithium and can use a kind of or mixture in the lithium salts such as lithium carbonate, oxygen lithia, lithium dihydrogen phosphate); Again by (5～20% of aforementioned total weight of material, weight ratio) adds carbon (carbon can be used a kind of or mixture in high-purity graphite powder, high-purity carbon black, the carbohydrate organic carbon), the material for preparing is sent into and is stirred flour mill and again stirred, disperse, grind 30 minutes～3 hours, makes material further mixed, grain refined, nanometer; Ground presoma material is sent into calciner carry out sintering reaction, control calcining materials temperature: (500～750 ℃), calcination time: (1～3) hour, after sintering is finished, (1～3) hour is stirred, ground to material cooling also again, analytical control, packing obtain the ferric phosphate lithium cell electrode material.
Compared with prior art, the invention has the beneficial effects as follows: the existing domestic and international method of raw materials for production cost can reduce by 50% or more (the existing used phosphorus of method source, source of iron flat fare are 8000 yuan/more than the t, the used by-product ferrophosphorus of this method average price is below the 2000 yuan/t); This method has also been utilized the metallic elements such as the vanadium of contained trace, manganese, chromium in the ferrophosphorus except adding the high purity graphite powder, the electrical efficiency of product, chemical property are improved greatly; Contain more Fe in the product of the present invention
2+Ion, the oxidation resistance of product is extremely strong; All round process need not nitrogen, argon atmospher protection, makes production process be simplified, make things convenient for, and cost further reduces; Because introduced more ferrous phosphate ion and three fine gtindings in the product, the product particulate is spared into positive sphere, tap density is greatly enhanced, and can be improved to specific capacity is corresponding; In the inventive method all round process, without fresh water (FW), produce without waste water,waste gas and industrial residue, energy-saving and emission-reduction, used grinding, calciner be simple in structure, control simple easily, good airproof performance, control of product quality easy reliable, be easy to mass, serialization production, solved well the problem that existing ferric phosphate lithium cell electrode material exists in producing and using.Product electrical performance indexes of the present invention: 0.2C specific discharge capacity＞150.0mAh/g, 1C specific discharge capacity＞142.2mAh/g, the 0.2C volume and capacity ratio reaches 203.75mAh/cm3, and tap density is 1.53～1.85g/cm3.
Embodiment
Embodiment one.
1. ferrophosphorus abrasive dust operation: ferrophosphorus is with just broken granular to about 3mm of hammer mill, levigate stand-by to the above fineness of 100 orders with stirring flour mill or ball mill, the Raymond mill ferrophosphorus about with 3mm again.
2. oxidizing roasting: the feed end of levigate ferrophosphorus powder being sent into stainless steel rotary kiln feeds in raw material, spray into fuel oil and hot-air (also can make be heated by resistive, inductance, microwave heating) from the discharge end of kiln, the ferrophosphorus powder is carried out oxygen oxygen uptake calcination, temperature of charge in the control stove: 700～800 ℃, roasting time: 2 hours, under stirring and the state of oxidation, make the oxygen uptake of ferrophosphorus powder, change into the mixture of ferrous phosphate and ferric phosphate.After roasting is finished, cool off for subsequent use.Before oxidizing roasting, the ferrophosphorus powder of the ferrophosphorus of not roasting and roasting can be carried out oxidizing roasting after by 1: 0.3～1 volume or weight ratio batching mixing, can improve the oxygen uptake roasting efficient minimizing roasting time of ferrophosphorus powder.Sintering temperature must not surpass 1000 ℃, otherwise the loss of phosphorus can increase.The washing of baking tail gases available water attracts to process, and can get phosphoric acid,diluted.
3. chemical examination: the ferrophosphorus powder that above-mentioned oxidizing roasting is good carries out phosphorus content, iron content analytical test.Such as phosphorous 18.54%; Iron content total amount 58.68%.
4. calculate phosphorus, lithium, the carbon amount added: (in oxidizing roasting ferrophosphorus powder 1000kg)
A. add the phosphorus amount: total iron amount 586.8kg * 0.555=325.67kg-185.4kg=140.27kg, to add the phosphoric acid of 85% content: 140.27kg ÷ 26.87% (phosphoric acid phosphorus content)=522.05kg (should add phosphoric acid amount).
B. add the lithium amount: by total iron amount 586.8kg * 0.124=72.76kg, lithium carbonate contains the lithium amount by 18.7686%, and quality is by 99.9%.Should add the lithium carbonate amount: 72.76kg ÷ 18.7686% ÷ 99.9%=388.07kg (should add the lithium carbonate amount).The food grade phosphoric acid 522.05kg that takes by weighing content 85% injects the enamel reactive tank, adds the lithium carbonate 388.07kg of content 99.9% under the room temperature in the phosphoric acid, adds several times, and lithium carbonate is reinforced too fast, and pot easily rises.And stirring is dissolved fully.Dissolve react completely after, the 1000kg ferrophosphorus powder that above-mentioned oxidizing roasting is finished and phosphorus, the fair minute mix and blend of lithium reaction solution are all even.Add high purity graphite powder 122.37kg, fair minute mix and blend is all even again, obtains ferric lithium phosphate precursor material to be sintered again.
C. add the carbon amount: press ferrophosphorus powder 1000kg+ and mend phosphorus amount 149.9kg+ benefit lithium 73.77kg=1223.67kg * 10% (mending carbon % number)=122.37kg (high purity graphite powder).
5. the sintering of presoma: the ferric lithium phosphate precursor of above-mentioned b material to be sintered is joined in the rotary furnace of lining stone China ink or carbon materials, use inductive heating, neutrality or micro-oxidizing atmosphere in the control stove, temperature of charge is 600～700 ℃ in the control stove, behind the calcination reaction 2 hours, cool to 80 ℃ and send into to stir in the mill with bottom discharge and with material and ground 2 hours, discharging, analytical control, packing obtain the ferric phosphate lithium cell electrode material.
Embodiment two.
1. ferrophosphorus abrasive dust: ferrophosphorus is with just broken granular to about 3mm of hammer mill, levigate stand-by to the above fineness of 100 orders with stirring flour mill or ball mill, the roller mill ferrophosphorus about with 3mm again.
2. oxidizing roasting: the feed end of the ferrophosphorus powder of 1 operation being sent into stainless steel rotary kiln feeds in raw material, spray into fuel oil and hot-air (also can make be heated by resistive, inductance, microwave heating) from discharge end, the ferrophosphorus powder is carried out the oxygen calcination, temperature of charge in the control stove: 700～800 ℃, roasting time: 3 hours, under stirring and the state of oxidation, under stirring and the state of oxidation, make the oxygen uptake of ferrophosphorus powder, change into the mixture of ferrous phosphate and ferric phosphate.Before oxidizing roasting, the ferrophosphorus powder of the ferrophosphorus of not roasting and roasting can be carried out oxidizing roasting after by 1: 0.3～1 volume or weight ratio batching mixing, can improve the oxygen uptake roasting efficient minimizing roasting time of ferrophosphorus powder.Sintering temperature must not surpass 1000 ℃, otherwise the loss of phosphorus can increase.Baking tail gases washes with water and attracts to process, and can get phosphoric acid,diluted.
3. chemical examination: the ferrophosphorus powder that above-mentioned oxidizing roasting is good carries out phosphorus content, iron content analytical test.Such as phosphorous 22.56%; Iron content total amount 54.86%.
4. calculate phosphorus, lithium, the carbon amount added: (in oxidizing roasting ferrophosphorus powder 1000kg)
A. add the phosphorus amount: total iron amount 548.6kg * 0.6=329.16kg (total phosphorus content)-225.6kg (content)=103.56kg (additional amount), to add the biphosphate ammonium: 103.56kg ÷ 26.93% (biphosphate phosphorus content 26.93%, contain (NH4H2PO4), 99.5%)=386.49kg (should add the ammonium dihydrogen phosphate amount).
B. add the lithium amount: by total iron amount 548.6kg * 0.15=82.29kg (adding the lithium amount), contain the lithium amount by 28.9% with lithium hydroxide, purity 99.9%.Answer hydro-oxidation lithium amount: 82.29kg ÷ 28.9% ÷ 99.9%=285.03kg (answering hydro-oxidation lithium amount).Take by weighing ferrophosphorus powder 1000kg, the ammonium dihydrogen phosphate 386.49kg that oxidizing roasting finishes, lithium hydroxide 285.03kg, the brown powdered sugar 237.17kg of content 99.9%, permit minute mix and blend all even with the stir mixing machine, obtain ferric lithium phosphate precursor material to be sintered.
C. add the carbon amount: mend phosphorus amount 103.56kgkg+ by ferrophosphorus powder 1000kg+ and mend lithium 82.29kg=1185.85kg (total amount) * 20% (mending carbon % number)=237.17kg (in brown sugar).
5. the sintering of presoma: above-mentioned ferric lithium phosphate precursor material to be sintered is joined in the rotary furnace of lining stone China ink or carbon materials, use inductive heating, neutrality or micro-oxidizing atmosphere in the control stove, temperature of charge is 650～750 ℃ in the control stove, behind the calcination reaction 3 hours, cool to 80 ℃ and send into to stir in the mill with bottom discharge and with material and ground 3 hours, discharging, analytical control, packing obtain the ferric phosphate lithium cell electrode material.
Claims (1)
1. the method for a ferrophosphorus preparing phosphoric acid lithium iron battery material, as raw material take yellow phosphorus by-product ferrophosphorus, add the process of phosphorus, lithium, carbon production ferric phosphate lithium cell electrode material, it is characterized in that: ferrophosphorus is just broken granular to 3mm, be ground to again particle diameter less than 100 orders after, carry out oxidizing roasting, control temperature: (600～1000 ℃), roasting time: (1.5～4) hour, before roasting, can carry out again oxidizing roasting behind the volume or weight ratio mixing of ferrophosphorus powder in (1: 0.3～1) with the ferrophosphorus powder of not roasting and roasting; Chemical equation: 4Fe
2P+8O
2→ 2Fe
3(PO
4)
2+ Fe
24Fe
2P+11O
2→ 4FePO
4+ 2Fe
2O
32Fe
2O
3+ 4H
3PO
4→ 4FePO
4+ 6H
2O; After the oxidizing roasting fully, according to (iron: phosphorus=1: 0.555～0.62; Iron: lithium=1: 0.124～0.18; All by the element wt ratio) ratio, in the roasting material, add P elements, elemental lithium; (adding P elements can be with the phosphoric acid of food-grade, a kind of or mixture in the ammonium phosphate salt, adds elemental lithium and can use a kind of or mixture in the lithium salts such as lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate); By 5～20% of aforementioned total weight of material, add carbon (carbon can be used a kind of or mixture in high-purity graphite powder, high-purity carbon black, the carbohydrate organic carbon), the material stirring for preparing, dispersion, grinding 30 minutes～3 hours; Ground material is sent into calciner carry out sintering reaction, control temperature of charge: (500～750 ℃), calcination time: (1～3) hour, after again stirring, grind (1～3) hour after the material cooling, analytical control, packing obtain the ferric phosphate lithium cell electrode material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017215131A1 (en) * | 2016-06-13 | 2017-12-21 | 四川大学 | Method for preparing lixfeypzo4 from ferrophosphorus |
| CN107792840A (en) * | 2017-10-27 | 2018-03-13 | 昆明理工大学 | A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate |
| CN110002419A (en) * | 2019-04-18 | 2019-07-12 | 王东升 | A kind of preparation method of high-tap density ferric phosphate |
| CN115285959A (en) * | 2022-07-06 | 2022-11-04 | 宜宾天原海丰和泰有限公司 | Low-cost continuous production method of iron phosphate |
-
2013
- 2013-07-16 CN CN2013103075560A patent/CN103367747A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017215131A1 (en) * | 2016-06-13 | 2017-12-21 | 四川大学 | Method for preparing lixfeypzo4 from ferrophosphorus |
| CN107792840A (en) * | 2017-10-27 | 2018-03-13 | 昆明理工大学 | A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate |
| CN110002419A (en) * | 2019-04-18 | 2019-07-12 | 王东升 | A kind of preparation method of high-tap density ferric phosphate |
| CN110002419B (en) * | 2019-04-18 | 2021-07-02 | 王东升 | Preparation method of high-tap-density iron phosphate |
| CN115285959A (en) * | 2022-07-06 | 2022-11-04 | 宜宾天原海丰和泰有限公司 | Low-cost continuous production method of iron phosphate |
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