CN102153063B - Method for preparing lithium iron phosphate serving as battery material from brown corundum slags - Google Patents
Method for preparing lithium iron phosphate serving as battery material from brown corundum slags Download PDFInfo
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- CN102153063B CN102153063B CN 201110079283 CN201110079283A CN102153063B CN 102153063 B CN102153063 B CN 102153063B CN 201110079283 CN201110079283 CN 201110079283 CN 201110079283 A CN201110079283 A CN 201110079283A CN 102153063 B CN102153063 B CN 102153063B
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- ferrous
- brown corundum
- solution
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- oxalic acid
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Abstract
The invention relates to a method for preparing lithium iron phosphate serving as a battery material from brown corundum slags, which comprises the following process steps of: 1, preparing ferrous sulphate crystals into solution, respectively carrying out preprocessing on the obtained solution and oxalic acid solution, slowly adding the preprocessed oxalic acid solution into the solution of ferrous sulphate to perform a reaction, and carrying out centrifugal separation, washing and drying to obtain powder ferrous oxalate; and 2, mixing ferrous oxalate, lithium hydroxide and diammonium hydrogen phosphate, placing the mixture into a planetary ball mill to carry out ball milling, transferring the ball-milled material into a tube resistance furnace, carrying out high temperature firing under the protection of the nitrogen environment and cooling the obtained product to the room temperature to obtain lithium iron phosphate. Compared with the prior art, the method has the beneficial effects that 1, the problems of generation of a great amount of ammonia gas to cause environment pollution, combustion, explosion and the like, which are generated in other synthesis methods because ammonium dihydrogen phosphate is used as the raw material, are avoided; 2, the raw material has stable supply and price; 3, the conductivity of a cathode material can be greatly improved; and 4, the method is easy to realize industrial large-scale production.
Description
Technical field
The invention belongs to new energy materials and recycling economy field, concrete relate to a kind of method of being produced the new energy materials LiFePO 4 by iron slag, particularly utilize the fused brown corundum slag to prepare the method for ferrous phosphate lithium battery material for raw material adopts acidleach reduction-synthetic-mechanical and chemical activation three-step approach.
Background technology
The LiFePO of quadrature olivine structural
4Positive electrode becomes new study hotspot both at home and abroad gradually.The advantages such as its high-temperature behavior and heat endurance obviously are better than other known positive electrode, have not contain noble element, and raw material is cheap, and resource is greatly abundant.The industrialization of this material and popularization and application are to reducing the lithium ion battery cost, improve battery security, enlarge the lithium ion battery industry, promote that lithium ion battery maximizes, high power has very great meaning, the application that makes lithium ion battery in middle large-capacity ups, medium-and-large-sized energy-storage battery, electric tool, electric automobile is become a reality.
LiFePO 4 material is that the Japanese discloses at first.1996, there is a subordinate DoCoMo telecommunications company of Japanese telephone and telegraph corporation (NTT) that government backs up to disclose first the anode material of lithium battery of olivine structural.Afterwards 1997, vertical professor Goodenough of university of Texas, USA just definite designation also applies for the ferric phosphate lithium cell patent of invention.More external mechanisms and expert register the patent of peroxophosphoric acid iron lithium really, but their LiFePO 4 material that just proves of registration can be used in the patent of field of batteries, and concrete application patent does not have.
The technology of China's ferric phosphate lithium cell patent consists of, rank analysis with the IPC classification, the IPC classification number that comes front 3 is respectively C01B25 (phosphorus, its compound), H01M4 (electrode of battery pack), H01M10 (secondary cell and manufacturing thereof), domestic patented technology consists of and mainly concentrates on LiFePO 4 material, material preparation method, battery structure aspect, is specifically related to utilize the patent application of iron slag comprehensive utilization preparation LiFePO 4 relatively less.
The preparation method of ferrousphosphate lithium material mainly contains high temperature solid-state method, hydrothermal synthesis method, liquid-phase coprecipitation, microwave heating method, sol-gal process, carbothermic method and mechanical and chemical activation method.The shortcomings such as high temperature solid-state method is the technology of the applicable large-scale production of present unique energy, and energy consumption is high, the cycle is long, phase is inhomogeneous but exist, and crystal irregular shape and size are larger; For the Hydrothermal Synthesis technology, exist the equilibrium problem of carbon and glue doping coupling; For the liquid phase coprecipitation method, need employing not make conductive additive with the metal oxide that LiFePO 4 reacts; For microwave heating method, product particle uniformity and powder morphology that this method makes are relatively poor, and the product capacitance is not high; The shortcoming preparation process of sol-gal process is complicated, and condition is harsh, and cost is high, and output is little, and the industrialization difficulty is larger; The carbothermic method synthesis condition is harsh, and the time is longer, and at present this technology basically the patent of U.S. Valence company and Japanese Sony company cover; The mechanical and chemical activation method is as one of fabrication of new materials technology, the aspects such as superconductor, high-temperature material have been widely used in, can obtain to be difficult under normal condition the synthetic new function material with special performance with the mechanochemistry technology, and have that cost is low, output is large, technique simply reaches the characteristics such as the cycle is short, has many advantages aspect synthesizing iron lithium phosphate.
Chinese patent CN1948135 discloses take lithium hydroxide, ferrous oxalate and ammonium dihydrogen phosphate (ADP) as raw material, with polychlorostyrene for alkene for covering the carbon carbon source, under normal temperature and pressure, fully mix in organic solvent or aqueous medium, roasting in non-oxidizing gas atmosphere after the compound drying, naturally cooling by sieving after mechanical disruption, obtain the lithium iron phosphate cathode material that needs.But the raw materials used ferrous oxalate of this method is expensive, is not suitable for large-scale industrial production.
Summary of the invention
Problem to be solved by this invention is to propose a kind of method of utilizing brown corundum slag to prepare the ferrous phosphate lithium battery material for above-mentioned prior art, various process operation parameters in this process optimization building-up process are to realizing the industrialization of LiFePO 4.
The present invention is that the solution that the problem of the above-mentioned proposition of solution adopts is: utilize brown corundum slag to prepare the method for ferrous phosphate lithium battery material, include following processing step:
1) the ferrous sulfate crystal is configured to copperas solution, gained copperas solution and oxalic acid solution used additives ammoniacal liquor, absolute ethyl alcohol respectively carry out pretreatment, pretreated oxalic acid solution is slowly joined in copperas solution react 30min under 30～40 ℃, centrifugation, washing and oven dry obtain the powdery ferrous oxalate;
2) with step 1) ferrous oxalate that makes and lithium hydroxide, diammonium hydrogen phosphate in molar ratio 1: 1-1.2: 1-1.5; mix and be placed in 500～700rpm planetary ball mill ball milling; the material that ball milling is good moves in tube type resistance furnace; the lower high temperature sintering of nitrogen environment protection is cooled to room temperature and gets final product to get LiFePO 4.
Press such scheme, step 1) preparation method of described ferrous sulfate crystal is: be 2.5～4 with brown corundum slag and sulfuric acid according to mass volume ratio, wherein mass unit is g, volume unit is ml, carry out the mix and blend reaction, leaching temperature is 60～80 ℃, and the reaction time is 5～8 hours, filter, add reduced iron powder no longer to contain Fe to filtrate in the filtrate that obtains after filter
3+Regulate filtrate pH value, add flocculant, carry out stirring operation, standing rear centrifugation removal of impurities obtains the ferrous sulfate supernatant, regulating ferrous sulfate supernatant pH is 1～2, be 65～75 ℃ in temperature and carry out evaporating, concentrating and crystallizing, 30～40 ℃ of vacuum drying 5～8 hours, obtain the ferrous sulfate crystal.
Press such scheme, the auxiliary leaching of microwave is adopted in described leaching.
Press such scheme, the mass percent concentration of described sulfuric acid is 25%～45%.
Press such scheme, described filtrate pH value is 4.5～5.5, to remove Al
3+
Press such scheme, described stirring operation refers at first rapid stirring 400～600r/min, time 30～60s, low rate mixing 30～80r/min then, time 5～15min.
Press such scheme, step 1) pretreated copperas solution and oxalic acid solution quality very concentration be 10～30%.
Press such scheme, step 2) described high temperature sintering refers to 400-800 ℃ of lower calcination 2～5 hours.
Press such scheme, step 2) also add additive zinc oxide in described mechanical milling process.
Technological reaction principle of the present invention:
Fe in the raw material slag is with Fe
2O
3Meter, with the iron of sulfuric acid to leach slag, reaction equation is: Fe
2O
3+ 3H
2SO
4→ Fe
2SO
4+ 3H
2O is with the Fe in iron powder reducing solution
3+, reaction equation is: Fe
2SO
3+ Fe → 3FeSO
4, then under the effect of auxiliary agent, ferrous sulfate and oxalic acid react: FeSO
4+ H
2C
2O
4=FeC
2O
4+ H
2SO
4, the high-purity oxalic acid ferrous iron that makes with previous reaction at last takes mechanochemical reaction to prepare LiFePO 4, and in preparation process, solid phase reaction mechanism can be divided into for three steps:
The first step is LiOH and (NH
4)
2HPO
4Chemical reaction occurs, and generates Li
3PO
4, the temperature of this step reaction is minimum, may just complete in mechanical milling process, as reaction equation (6-1);
(NH
4)
2HPO
4+LiOH→Li
3PO
4(s)+NH
3(g)+H
2O(g)(6-1)
Second step is remaining (NH
4)
2HPO
4With FeC
2O
4H
2O reacts, and obtains a kind of middle phase (inter), and Average molecular formula should be Fe
3(PO
4)
2, it is also Fe under 800 ℃
3(PO
4)
2, this step reaction should be completed 400 ℃ of left and right, as reaction equation (6-2);
(NH
4)
2HPO
4+FeC
2O
4·2H
2O→
NH
3(g)+H
2O(g)+CO
2(g)+Fe
3(PO
4)
2(6-2)
The 3rd step was Li
3PO
4With the inter reaction, finally generate LiFePO
4, this step reaction until 800 ℃ just can finish, as reaction equation (6-3).
Li
3PO
4+Inter→LiFePO
4 (6-3)
The present invention is with respect to the beneficial effect of prior art:
(1) solid phase reaction is raw materials used is diammonium hydrogen phosphate, has avoided using in other synthetic method ammonium dihydrogen phosphate (ADP) to be raw material, produces a large amount of ammonia contaminated environment and the problems such as burning, blast;
(2) raw material sulphuric acid that adopts, iron powder, ammoniacal liquor, absolute ethyl alcohol, oxalic acid, diammonium hydrogen phosphate etc. are large chemical products, in the supply of raw material and all highly stable in price;
(3) use the mechanical and chemical activation method, additive zinc oxide and lithium source, source of iron, phosphorus source is reached fully mixes, additive namely can play a protective role in follow-up reaction, also can form the coating function to lithium iron phosphate particles, can greatly improve the electric conductivity of positive electrode;
(4) process route that adopts is easily controlled, and technology stability is good, easily realizes producing in enormous quantities; Process Route Planning is simple, and mechanical and chemical activation method synthetic method is easy and simple to handle, and technological parameter is easy to control, and the material property of preparation is stable, is easy to realize large-scale industrialization production;
(5) due to the cheap large chemical products of present technique route usage comparison, and utilize the ferrous and ferrous oxalate of homemade high-purity sulfuric acid to be synthesis material, cost be other technique costs of raw material half even 1/3, have the market competitiveness;
(6) the present invention adopts the ferrousphosphate lithium material correlated performance of mechanical and chemical activation method novel process development to meet or exceed imported product in earlier stage.
Description of drawings
Fig. 1 is iron slag comprehensive utilization preparation LiFePO
4Process route;
Fig. 2 is the technological process of brown corundum slag preparing high-purity ferrous sulfate;
Fig. 3 is that ferrous sulfate prepares the ferrous technological process of high-purity oxalic acid;
Fig. 4 is that mechanochemical reaction prepares the LiFePO 4 technological process;
Fig. 5 is the LiFePO 4 XDR collection of illustrative plates that embodiment 1 makes;
Fig. 6 is the LiFePO 4 SEM collection of illustrative plates that embodiment 1 makes.
The specific embodiment
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Be that 25% sulfuric acid is 3.0 by mass volume ratio with 40g palm fibre corundum slag and mass percent concentration, mix and blend reaction in conical flask, leach under 70 ℃ of waters bath with thermostatic control, reaction time is 5 hours, filtration under diminished pressure adds appropriate reduced iron powder (excessive a little) to continue stirring reaction a period of time until do not contain Fe in filtrate
3+(thiocyanic acid by check), filtration under diminished pressure, regulating filtrate pH value with calcium oxide is that 4.5～5.5 (purpose is to remove Al
3+), add 2ml mass fraction 1%PAM solution, rapid stirring (450r/min) 30s, low rate mixing (60r/min) 10min, standing rear centrifugation removal of impurities, get supernatant and regulate pH to 1～2,70 ℃ lower evaporating, concentrating and crystallizing, it is 99.3% (mass percent) ferrous sulfate crystal that 30 ℃ of lower vacuum drying 6h make purity;
With the above-mentioned 14gFeSO that makes
47H
2O is configured to solution with the water-soluble solution of 15ml, adds the 6ml pretreatment with agueous Ammonia, mixes standby.6.5g oxalic acid with the water-soluble solution of 25ml, is added the pretreatment of 40ml absolute ethyl alcohol, mix standby.Under stirring condition, the oxalic acid solution of handling well is dripped in copperas solution, reaction temperature is 40 ℃, the reinforced warm reaction of the follow-up continuation of insurance 30min that completes, generate faint yellow ferrous oxalate crystallization, then with the material centrifugation, washing, oven dry obtains that purity is 99.1%, average grain diameter is 5.0 μ m ferrous oxalate powder under 40 ℃;
Lithium hydroxide, ferrous oxalate, diammonium hydrogen phosphate 1: 1: 1 are in molar ratio mixed, and after mixing, material is 20g, is 3.0 to mix that to be placed in planetary ball mill be 650rpm ball milling 6h at rotating speed by ratio of grinding media to material.Then the material with milled moves in tube type resistance furnace, 700 ℃ of high temperature sinterings reaction 4h under nitrogen environment protection, and being cooled to room temperature, can to obtain average grain diameter be 9.4077 μ m LiFePO 4 products.
Embodiment 2
Obtain LiFePO according to the method identical with embodiment 1
4Product, different is to adopt the auxiliary acidleach of microwave in brown corundum slag leaching stage, leaching liquid is mass percent 25% sulfuric acid solution, the mass volume ratio of palm fibre corundum slag and sulfuric acid is 4, and microwave intensity is to leach 30min under moderate heat (450W) condition, and the iron leaching rate can reach 98%.
Embodiment 3
Obtain LiFePO according to the method identical with embodiment 1
4Product, different is, at synthetic LiFePO
4In the stage, changing rotating speed is that the 700rpm ball milling mixes, and 700 ℃ of high-temperature calcination 3h obtain LiFePO
4Product.
Embodiment 4
Obtain LiFePO according to the method identical with embodiment 1
4Product, different is, at synthetic LiFePO
4In the stage, adding a small amount of zinc oxide is that the 700rpm ball milling mixes as additive at rotating speed, and 700 ℃ of high-temperature calcination 3h obtain LiFePO
4Product.
Embodiment 5
Obtain LiFePO according to the method identical with embodiment 1
4Product, different is, at synthetic LiFePO
4In the stage, adding a small amount of zinc oxide is that the 650rpm ball milling mixes as additive at rotating speed, and 700 ℃ of high-temperature calcination 4h obtain LiFePO
4Product.
Embodiment 6
Obtain LiFePO according to the method identical with embodiment 1
4Product, different is, at synthetic LiFePO
4In the stage, adding a small amount of zinc oxide is that the 650rpm ball milling mixes as additive at rotating speed, and 700 ℃ of high-temperature calcination 5h obtain LiFePO
4Product.
Bound value, the interval value of the technological parameter (as temperature, time etc.) that the present invention is cited can be realized the present invention, do not enumerate embodiment at this.
Claims (4)
1. utilize brown corundum slag to prepare the method for ferrous phosphate lithium battery material, include following processing step:
1) be 2.5 ~ 4 with brown corundum slag and sulfuric acid according to mass volume ratio, wherein mass unit is g, volume unit is ml, carry out the mix and blend reaction, adopt the auxiliary leaching of microwave, the mass percent concentration of sulfuric acid is 25% ~ 45%, leaching temperature is 60 ~ 80 ℃, reaction time is 5 ~ 8 hours, filters, and adds reduced iron powder no longer to contain Fe to filtrate in the filtrate that obtains after filter
3+, regulating filtrate pH value is 4.5 ~ 5.5, to remove Al
3+, add flocculant, carry out stirring operation, described stirring operation refers at first rapid stirring 400～600r/min, time 30～60s, low rate mixing 30～80r/min then, time 5～15min, standing rear centrifugation removal of impurities, obtain the ferrous sulfate supernatant, regulating ferrous sulfate supernatant pH is 1 ~ 2, is 65 ~ 75 ℃ in temperature and carries out evaporating, concentrating and crystallizing, 30 ~ 40 ℃ of vacuum drying 5 ~ 8 hours, obtain the ferrous sulfate crystal; The ferrous sulfate crystal is configured to copperas solution, gained copperas solution and oxalic acid solution used additives ammoniacal liquor, absolute ethyl alcohol respectively carry out pretreatment, pretreated oxalic acid solution is slowly joined in copperas solution react 30min under 30 ~ 40 ℃, centrifugation, washing and oven dry obtain the powdery ferrous oxalate;
2) ferrous oxalate that step 1) is made and lithium hydroxide, diammonium hydrogen phosphate be 1:1-1.2:1-1.5 in molar ratio; mix and be placed in 500 ~ 700rpm planetary ball mill ball milling; the material that ball milling is good moves in tube type resistance furnace; the lower high temperature sintering of nitrogen environment protection is cooled to room temperature and gets final product to get LiFePO 4.
2. prepare the method for ferrous phosphate lithium battery material by the brown corundum slag of utilization claimed in claim 1, it is characterized in that the pretreated copperas solution of step 1) and oxalic acid solution mass percentage concentration are 10 ~ 30%.
3. preparing the method for ferrous phosphate lithium battery material by the brown corundum slag of the described utilization of claim 1 or 2, it is characterized in that step 2) described high temperature sintering refers to 400-800 ℃ of lower calcination 2 ~ 5 hours.
4. prepare the method for ferrous phosphate lithium battery material by the brown corundum slag of the described utilization of claim 1 or 2, it is characterized in that step 2) also add additive zinc oxide in described mechanical milling process.
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| CN105129761A (en) * | 2015-08-31 | 2015-12-09 | 无锡市嘉邦电力管道厂 | Method for preparing ferrous phosphate positive pole material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101339995A (en) * | 2008-08-12 | 2009-01-07 | 中国兵器工业第二一三研究所 | Preparation of lithium iron phosphate positive electrode material for lithium ion power cell |
| CN101624650A (en) * | 2009-08-04 | 2010-01-13 | 长沙达华矿业技术开发有限公司 | Microwave irradiation-acid leaching vanadium-recovering process of stone coal containing vanadium |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101339995A (en) * | 2008-08-12 | 2009-01-07 | 中国兵器工业第二一三研究所 | Preparation of lithium iron phosphate positive electrode material for lithium ion power cell |
| CN101624650A (en) * | 2009-08-04 | 2010-01-13 | 长沙达华矿业技术开发有限公司 | Microwave irradiation-acid leaching vanadium-recovering process of stone coal containing vanadium |
Non-Patent Citations (3)
| Title |
|---|
| 张大维 等.刚玉渣回收镓、铁和铝的试验研究.《矿产综合利用》.1997,(第3 期),第1节、第2.2节、图2. * |
| 张莉 等.高铁脱硫渣制备高纯度草酸亚铁的研究.《武汉工程大学学报》.2010,第32卷(第7期),第1.2节第2.2节、图1、图2. * |
| 郭静.锂离子电池正极材料LiFePO4的合成及电化学性能研究.《中国优秀硕士学位论文全文数据库（电子期刊）工程科技II辑》.2008,(第12期),第19页第2.3.1节. * |
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