CN103094579B - Method for preparing cathode material-lithium iron phosphate of lithium ion battery by utilizing steel slag - Google Patents

Method for preparing cathode material-lithium iron phosphate of lithium ion battery by utilizing steel slag Download PDF

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CN103094579B
CN103094579B CN201310029020.7A CN201310029020A CN103094579B CN 103094579 B CN103094579 B CN 103094579B CN 201310029020 A CN201310029020 A CN 201310029020A CN 103094579 B CN103094579 B CN 103094579B
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slag
water
lithium
filter cake
steel slag
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CN103094579A (en
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刘新保
贾晓林
陈晨
蔡俊明
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ZHENGZHOU DELANGNENG BATTERY CO Ltd
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a method for preparing a cathode material-lithium iron phosphate of a lithium ion battery by utilizing steel slag. The method comprises the steps as follows: mixing the steel slag with a water-soluble carbon source compound water solution, and carrying out microwave heat treatment, reduction and magnetic separation to obtain a steel slag extract; reacting the steel slag extract with a mixed solution of diluted sulfuric acid, hydrogen peroxide and phosphoric acid, and extracting to obtain a calcium-free steel slag filter cake; adding lithium carbonate and the water-soluble carbon source compound water solution into the filter cake to obtain a precursor; and carrying out microwave sintering on the precursor to obtain the cathode material-lithium iron phosphate. Part of conventional raw materials are replaced with the steel slag as raw materials, so that the cost can be reduced by more than 30% and the obtained product is good in cycle performance; the conventional processes of ball-milling, drying and the like are removed, so that the process and the control operation are simple, inert gas does not need to be used in the sintering process, harmful gas such as nitrogen oxide and the like is not generated, the pollution is avoided, and the environment is protected; and the method is widely suitable for industrial production.

Description

Utilize the method for prepared from steel slag for lithium ion battery anode material lithium iron phosphate
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, particularly relate to one and utilize slag to prepare anode material for lithium-ion batteries LiFePO by microwave thermal processing 4method.
background technology
Along with the fast development of Chinese national economy, the contradiction of shortage of resources, ambient pressure is increasing.Developing Circulation Economy, raising resource utilization, be the inevitable approach that solves current china natural resources, environmental constraints economic development, need to improve energetically the comprehensive utilization ratio of first resource, develops secondary resource simultaneously.A kind of industrial solid wastes of blast furnace slag, are the slags of discharging in blast furnace ironmaking process, claim again blast-furnace cinder.Chinese large-sized steel mill is more, annual blast furnace slag discharge capacity is huge, only there is small part to be secondary use, approximately 4,000,000 tons of the blast furnace slags discharging as annual in Baogang, be used for the Year's consumption of slag cement 800,000 tons of left and right, approximately 3,200,000 tons of air storages of annual residue, need to take tract when stacking, work the mischief to biological environment.In slag, except the essential elements such as Ca, Si, Mg, P, Fe, O, also contain a small amount of metallic element such as Mn, V, Cr, Ni, Nb.How slag is made full use of, extract useful element wherein, and then prepare the technical barrier that anode material for lithium-ion batteries is needs solution.
Research shows, utilizing metal ion mixing processing is to improve anode material for lithium-ion batteries LiFePO 4one of effective means of conductivity, the doping of a lot of metal ions is to anode material for lithium-ion batteries LiFePO 4the raising of conductivity has better effect.
Summary of the invention
the technical problem to be solved in the present invention:overcome anode material for lithium-ion batteries LiFePO in prior art 4cost is high, the shortcoming of poor performance, provides one to utilize discarded object slag for primary raw material, prepares anode material for lithium-ion batteries LiFePO 4method, the method cost and energy consumption are low, work simplification, and the positive electrode charge/discharge capacity making is high, good cycle, can be widely used in suitability for industrialized production.
technical scheme of the present invention:
One utilizes prepared from steel slag for anode material for lithium-ion batteries LiFePO 4method, comprise the following steps:
(1) take slag and pulverize, taking water-soluble carbon-source cpd of slag weight 3-8% and the water of 10-20%, water-soluble carbon-source cpd is added to the water and is stirred, obtaining the aqueous solution of carbon-source cpd; The aqueous solution of carbon-source cpd is added in slag, stir, obtain compound;
(2) compound is put into non-metallic vessel, then send into industrial microwave oven, reduce through microwave thermal processing; The product obtaining is carried out to magnetic separation, obtain slag extract;
(3) press the weight ratio metering dilute sulfuric acid of slag extract, 30-35wt% dilute sulfuric acid 1:3-5, slag extract is added in dilute sulfuric acid, stirring reaction 2-4h at 80-90 DEG C, through leaving standstill, suction filtration, washing obtain filtrate; Be the phosphoric acid of 85 wt% to adding the hydrogen peroxide of slag extract weight 20-30% and 30-40% concentration in filtrate, stir, isothermal reaction 4-5h at 40-50 DEG C, then regulate the pH value of reactant liquor to 3.0-5.0, after pH is stable, continue to stir 25-30 min, leave standstill 24-36h, wash, suction filtration, obtain the slag filter cake after deliming, the water content of the slag filter cake after described deliming is 15 wt %;
(4) to the phosphoric acid that adds lithium carbonate and 85 wt % in slag filter cake, the weight ratio of slag filter cake, lithium carbonate, phosphoric acid is 1:0.229-0.240:0.1016-0.1036, mixes, and obtains the mixture of slag filter cake, lithium carbonate and phosphoric acid;
(5) taking the weight of lithium carbonate as benchmark, the water of the metering water-soluble carbon-source cpd of 30-50% and 70-90%; Water-soluble carbon-source cpd is added to the water, stirs, obtain the aqueous solution of carbon-source cpd; The aqueous solution of carbon-source cpd is joined in the mixture of slag filter cake, lithium carbonate and phosphoric acid of step (4), stir, obtain presoma;
(6) by described presoma ageing 24-36h, be placed in non-metallic vessel, then put into industrial microwave oven and under air-tight state, carry out microwave sintering, prepare described anode material for lithium-ion batteries LiFePO 4.
2, the anode material for lithium-ion batteries LiFePO for preparing according to claim 1 4method, it is characterized in that: water-soluble carbon-source cpd described in described step (1), step (5) is one or more in oxalic acid, citric acid, glucose, sucrose, lactose, maltose.
Non-metallic vessel in described step (2), step (6) is silicon carbide crucible, graphite crucible or alumina crucible.
In described step (2), the power output of industrial microwave oven is 10-20KW, and microwave thermal processing is to be warming up to 550-650 DEG C with the speed of 2-10 per minute DEG C, and is incubated 10-15min at this temperature.
In described step (6), the power output of industrial microwave oven is 10-20KW, and microwave sintering is to be warming up to 600-700 DEG C with the speed of 2-10 per minute DEG C, and is incubated 20-35min at this temperature.
Magnetic field intensity when described magnetic separation is 30-95KA/m.
positive beneficial effect of the present invention:
(1) the present invention, by slag discarded object after removal of impurities is extracted, is used in battery raw material and substitutes the conventional raw materials such as iron, phosphorus and doped chemical, and the method can obviously reduce cost of material, reduces cost of material more than 30%; On the other hand, the method is utilized industrial solid castoff slag in a large number, turns waste into wealth, and is beneficial to and reduces environmental protection input, is beneficial to exploitation secondary resource, meets the national industrial policies of recycling economy, great to the question meaning of the current shortage of resources of alleviation China.
(2) the present invention adopts industrial microwave that the weak magnetic substance in slag is reduced to ferromagnetic substance, realizes separation by magnetic separation, the phosphorus in slag is effectively separated and is utilized simultaneously, has really realized the secondary utilization to trade waste.
(3) the present invention directly mixes the slag extract after deliming with the aqueous solution of lithium carbonate, carbon-source cpd, not only batch mixing is even, and the paste presoma obtaining further reacts between composition in mixed process, be conducive to the synthetic of positive electrode and carrying out that carbon is coated.
(4) the present invention has omitted ball milling, the dry run in traditional positive electrode preparation technology, work simplification, and control procedure is simple, can effectively ensure the quality of product; In sintering process, carbon-source cpd plays coated carbon, and sintering process does not need blanketing with inert gas, has further reduced production cost; sintering process produces without pernicious gases such as oxynitrides simultaneously; pollution-free, be conducive to environmental protection, can be widely used in suitability for industrialized production.
(5) the present invention adopts industrial microwave processing slag advantage obvious, and microwave is directly absorbed by slag, and reaction can accurately be controlled, and firing rate is fast, saves the reaction time, the sample grain refinement, the even structure that obtain.
(6) the present invention directly adulterates after extracting by carbon coated with by the metallic element in slag, in increasing substantially LiFePO4 conductivity, has effectively improved charge/discharge capacity and the cycle-index of positive electrode, and the quality of product is better.Referring to Fig. 3, Fig. 4.
Performance test: by the LiFePO of preparation 4mix by the weight ratio of 80:10:10 with acetylene black, Kynoar, add wherein appropriate organic solvent NMP(N-methyl pyrrolidone) be dissolved into pasty state, then pastel is evenly coated on aluminium foil, after 120 DEG C of vacuumize as anode, adopt lithium sheet as negative pole, polyethene microporous membrane Celgard 2400 is barrier film, and electrolyte adopts 1 molL -1liPF 6/ EC+DMC(is ethylene carbonate and dimethyl carbonate), in the glove box that is full of argon gas, be assembled into experimental cell, for charge-discharge test.Adopt LAND battery test system to discharge and recharge with the electric current of 20 mA/g at normal temperatures, in the voltage range of 2.5-4.1V to LiFePO 4the charge/discharge capacity of positive electrode and cycle life test.
After measured, when product of the present invention at room temperature discharges and recharges with the electric current of 20 mA/g, discharge capacity is 136-141.6mAh/g first, after 10 circulations, is 132.5-135.8mAh/g, shows good cycle performance.
Brief description of the drawings
Fig. 1: the XRD collection of illustrative plates of extract after slag deliming;
Fig. 1 can find out, extract fits like a glove with the XRD figure of conventional synthetic ferric phosphate precursor.
Fig. 2: the XRD figure of the extract after slag deliming after 680 DEG C of sintering;
Fig. 2 can find out, by the extract after slag deliming after heat treatment, has obtained very pure Fe 7(PO 4) 6, other element there is no appearance.
Fig. 3: sample LiFePO prepared by the present invention 4xRD figure;
In Fig. 3, do not see the diffraction maximum that contains other phase, this is little owing to leaving over the amount of other element in slag, has obtained very pure LiFePO 4sample.
Fig. 4: sample LiFePO prepared by the present invention 4scanning electron microscope (SEM) photograph;
Fig. 4 can find out, sample particle is tiny, and distribution of particles is more even, and maximum particle is 5 μ m left and right.
Embodiment
embodiment mono-: utilize prepared from steel slag for anode material for lithium-ion batteries LiFePO 4method, comprise the following steps:
(1) take 80 Kg slags, be ground into granularity and be less than 100 object powders; Take 4Kg glucose, add 10 Kg water, stirring and dissolving, obtains D/W; D/W is added in slag powder, put into mixer and stir, obtain compound; Wherein the chemical composition of slag is in table 1, lower same;
Table 1: the chemical composition (mass fraction %) of slag
Composition CaO FeO Al 2O 3 SiO 2 MgO MnO P 2O 5
Content 30-60 15-26 3-8 8-23 4-9 5-10 0.5-2
(2) compound of preparation is put into silicon carbide crucible, then send in industrial microwave oven, utilize microwave to be warming up to 550 DEG C with the speed of 10 DEG C per minute, and keep 15min at this temperature; Magnetic separation in the magnetic separation tube that is 45KA/m in magnetic field intensity by the reduzate obtaining, selects slag extract 30Kg;
(3) the dilution heat of sulfuric acid 100Kg of 30wt% is joined in slag extract to stirring reaction 4h at 80 DEG C; Leave standstill 1h, then suction filtration, washing obtain filtrate, and in filtrate, adding 8Kg hydrogen peroxide, 10Kg concentration is the phosphoric acid of 85 wt %, stir, 40 DEG C of reaction 4h of constant temperature, by NaOH solution adjusting pH value to 4.0, after pH is stable, continue to stir 25 min, leave standstill 24h, go to suction filtration, washing, obtain filter cake (water content 15%, be the slag extract after deliming), Fig. 1 is shown in by the XRD collection of illustrative plates of filter cake;
(4) take 10Kg filter cake, add the phosphatase 11 .036Kg of lithium carbonate 2.39Kg and 85wt%, obtain the mixture of filter cake, lithium carbonate and phosphoric acid;
(5) metering 1.0Kg citric acid, 2.0Kg water, be added to the water citric acid, stirs, and obtains aqueous citric acid solution; Aqueous citric acid solution is joined in the mixture of filter cake, lithium carbonate and phosphoric acid in step (4), stir, obtain presoma;
(6) by presoma ageing 24h, be then placed in silicon carbide crucible, crucible is put into microwave oven, be warming up to 680 DEG C with the speed of 5 DEG C per minute, at this temperature, keep 25min, prepare LiFePO 4.
embodiment bis-: utilize prepared from steel slag for anode material for lithium-ion batteries LiFePO 4method, comprise the following steps:
(1) take 80 Kg slags, be ground into granularity and be less than 100 object powders; Take 3Kg citric acid, add 8 Kg water, stirring and dissolving, obtains aqueous citric acid solution; Aqueous citric acid solution is added in slag powder, stir and obtain compound;
(2) compound of preparation is put into alumina crucible, send into industrial microwave oven and utilize microwave to be warming up to 600 DEG C with the speed of 8 DEG C per minute, at this temperature, keep 12min; Magnetic separation in the magnetic separation tube that is 35KA/m in magnetic field intensity by the reduzate obtaining, selects slag extract 30Kg;
(3) the dilution heat of sulfuric acid 100Kg of 30wt% is added in slag extract to stirring reaction 4h at 80 DEG C; Leave standstill 1h, then after suction filtration, washing, obtain filtrate, in filtrate, adding 6Kg hydrogen peroxide, 9Kg concentration is the phosphoric acid of 85 wt %, stir, 40 DEG C of reaction 4h of constant temperature, by NaOH solution adjusting pH value to 3.0, after pH is stable, continue to stir 25 min, after leaving standstill 24h, go to suction filtration, washing, obtain filter cake (water content 15%, i.e. slag extract after deliming);
(4) take 10Kg filter cake, adding the lithium carbonate of 2.32Kg and 1.026Kg concentration is the phosphoric acid of 85 wt %, obtains the mixture of filter cake, lithium carbonate and phosphoric acid;
(5) metering 0.90Kg sucrose and 1.80Kg water, be added to the water sucrose, stirs and obtain sucrose solution; Sucrose solution is joined in the mixture of filter cake, lithium carbonate and phosphoric acid of step (4), stir, obtain presoma;
(6) by presoma ageing 24h, be then placed in alumina crucible, crucible is put into industrial microwave oven, be warming up to 650 DEG C with the speed of 6 DEG C per minute, at this temperature, keep 15min, prepare LiFePO 4.
embodiment tri-: utilize prepared from steel slag for anode material for lithium-ion batteries LiFePO 4method, comprise the following steps:
(1) take 90 Kg slags, be ground into granularity and be less than 100 object powders; Take 4Kg oxalic acid, add 10 Kg water, stirring and dissolving, obtains oxalic acid aqueous solution; Oxalic acid aqueous solution is added in slag powder, stir and obtain compound;
(2) compound of preparation is put into alumina crucible, and send in industrial microwave oven, utilize microwave to be warming up to 600 DEG C with the speed of 10 DEG C per minute, and keep 15min at this temperature; Magnetic separation in the magnetic separation tube that is 55KA/m in magnetic field intensity by the reduzate obtaining, selects slag extract 40Kg;
(3) the dilution heat of sulfuric acid 120Kg of 30wt% is joined in slag extract to stirring reaction 4h at 80 DEG C; Leave standstill 1h, then after suction filtration, washing, obtain filtrate, in filtrate, adding 12Kg hydrogen peroxide, 16Kg concentration is the phosphoric acid of wt 85%, stir, and 40 DEG C of reaction 4h of constant temperature, by NaOH solution adjusting pH value to 5.0, after pH is stable, continue to stir 25 min, after standing 24h, go to suction filtration, washing, obtain filter cake (water content 15%, i.e. slag extract after deliming);
(4) get 10Kg filter cake, add the phosphoric acid that 2.35Kg lithium carbonate and 1.016Kg concentration are 85%, obtain the mixture of filter cake, lithium carbonate and phosphoric acid;
(5) measure the glucose of 0.6Kg, the citric acid of 0.6Kg, then add the water of 2.10Kg, stir, obtain glucose, lemon aqueous acid; Glucose, lemon aqueous acid are joined in the mixture of filter cake, lithium carbonate and phosphoric acid of step (4), stir, obtain presoma;
(6) by presoma ageing 24h, be then placed in alumina crucible, crucible is put into microwave oven, be warming up to 620 DEG C with the speed of 3 DEG C per minute, at this temperature, keep 35min, prepare LiFePO 4.
embodiment tetra-: and embodiment mono-is basic identical, difference is following steps:
(1) take 100 Kg slags, pulverize; Take 8Kg lactose, add 20 Kg water, stirring and dissolving, obtains lactose solution; Lactose solution is added in slag powder, stir, obtain compound;
(2) compound of preparation is put into graphite crucible, industrial microwave oven is warming up to 650 DEG C with the speed of 2 DEG C per minute while intensification, at this temperature, keeps 10min; Magnetic separation in the magnetic separation tube that is 95KA/m in magnetic field intensity by the reduzate obtaining, selects slag extract 40Kg;
(3) the dilution heat of sulfuric acid 100Kg of 35wt% is added in slag extract to stirring reaction 2h at 90 DEG C; Leave standstill 1h, then suction filtration, washing obtain filtrate, and in filtrate, adding 10Kg hydrogen peroxide, 15Kg concentration is the phosphoric acid of 85 wt %, stirs, 50 DEG C of reaction 5h of constant temperature, regulate the pH value to 4.0 of reactant liquor, after pH is stable, continue to stir 30 min, leave standstill 36h, go to suction filtration, washing, obtain filter cake (water content 15%, i.e. slag extract after deliming);
(4) take 10Kg filter cake, add the phosphatase 11 .020Kg of lithium carbonate 2.35Kg and 85wt%, obtain the mixture of filter cake, lithium carbonate and phosphoric acid;
(5) metering 1.0Kg lactose, 2.0Kg water, be added to the water lactose, stirs, and obtains lactose aqueous solution; Lactose aqueous solution is joined in the mixture of filter cake, lithium carbonate and phosphoric acid in step (4), stir, obtain presoma;
(6) by presoma ageing 30h, be then placed in graphite crucible, crucible is put into microwave oven, be warming up to 700 DEG C with the speed of 2 DEG C per minute, at this temperature, keep 20min, prepare LiFePO 4.
embodiment five: and embodiment mono-is basic identical, difference is following steps:
(1) take 100 Kg slags, pulverize; Take 8Kg maltose, add 15 Kg water, stirring and dissolving, obtains maltose solution; Maltose solution is added in slag powder, stir, obtain compound;
(2) compound of preparation is put into graphite crucible, be warming up to 600 DEG C with the speed of 5 DEG C per minute with industrial microwave oven, and keep 12min at this temperature; Magnetic separation in the magnetic separation tube that is 80KA/m in magnetic field intensity by the reduzate obtaining, selects slag extract 30Kg;
(3) the dilution heat of sulfuric acid 100Kg of 35wt% is joined in slag extract to stirring reaction 3h at 85 DEG C; Leave standstill 2h, then suction filtration, washing obtain filtrate, and in filtrate, adding 7Kg hydrogen peroxide, 10Kg concentration is the phosphoric acid of 85 wt %, stirs, 45 DEG C of reaction 5h of constant temperature, regulate the pH value to 4.0 of reactant liquor, after pH is stable, continue to stir 30 min, leave standstill 30h, go to suction filtration, washing, obtain filter cake (water content 15%, i.e. slag extract after deliming);
(4) take 10Kg filter cake, add the phosphatase 11 .030Kg of lithium carbonate 2.30Kg and 85wt%, obtain the mixture of filter cake, lithium carbonate and phosphoric acid;
(5) metering 1.0Kg maltose, 2.0Kg water, be added to the water maltose, stirs, and obtains maltose solution; Maltose solution is joined in the mixture of filter cake, lithium carbonate and phosphoric acid in step (4), stir, obtain presoma;
(6) by presoma ageing 30h, be then placed in graphite crucible, crucible is put into microwave oven, be warming up to 680 DEG C with the speed of 5 DEG C per minute, at this temperature, keep 30min, prepare LiFePO 4.

Claims (4)

1. one kind is utilized prepared from steel slag for anode material for lithium-ion batteries LiFePO 4method, it is characterized in that: the method comprises the following steps:
(1) take slag and pulverize, taking water-soluble carbon-source cpd of slag weight 3-8% and the water of 10-20%, water-soluble carbon-source cpd is added to the water and is stirred, obtaining the aqueous solution of carbon-source cpd; The aqueous solution of carbon-source cpd is added in slag, stir, obtain compound;
(2) compound is put into non-metallic vessel, then send into industrial microwave oven, reduce through microwave thermal processing; The product obtaining is carried out to magnetic separation, obtain slag extract; The power output of described industrial microwave oven is 10-20KW, and microwave thermal processing is to be warming up to 550-650 DEG C with the speed of 2-10 per minute DEG C, and is incubated 10-15min at this temperature;
(3) press the weight ratio metering dilute sulfuric acid of slag extract, 30-35wt% dilute sulfuric acid 1:3-5, slag extract is added in dilute sulfuric acid, stirring reaction 2-4h at 80-90 DEG C, through leaving standstill, suction filtration, washing obtain filtrate; Be the phosphoric acid of 85 wt% to adding the hydrogen peroxide of slag extract weight 20-30% and 30-40% concentration in filtrate, stir, isothermal reaction 4-5h at 40-50 DEG C, then regulate the pH value of reactant liquor to 3.0-5.0, after pH is stable, continue to stir 25-30 min, leave standstill 24-36h, wash, suction filtration, obtain the slag filter cake after deliming, the water content of the slag filter cake after described deliming is 15 wt %;
(4) to the phosphoric acid that adds lithium carbonate and 85 wt % in slag filter cake, the weight ratio of slag filter cake, lithium carbonate, phosphoric acid is 1:0.229-0.240:0.1016-0.1036, mixes, and obtains the mixture of slag filter cake, lithium carbonate and phosphoric acid;
(5) taking the weight of lithium carbonate as benchmark, the water of the metering water-soluble carbon-source cpd of 30-50% and 70-90%; Water-soluble carbon-source cpd is added to the water, stirs, obtain the aqueous solution of carbon-source cpd; The aqueous solution of carbon-source cpd is joined in the mixture of slag filter cake, lithium carbonate and phosphoric acid of step (4), stir, obtain presoma;
(6) by described presoma ageing 24-36h, be placed in non-metallic vessel, then put into industrial microwave oven and under air-tight state, carry out microwave sintering, prepare described anode material for lithium-ion batteries LiFePO 4; The power output of described industrial microwave oven is 10-20KW, and microwave sintering is to be warming up to 600-700 DEG C with the speed of 2-10 per minute DEG C, and is incubated 20-35min at this temperature.
2. the anode material for lithium-ion batteries LiFePO for preparing according to claim 1 4method, it is characterized in that: water-soluble carbon-source cpd described in described step (1), step (5) is one or more in oxalic acid, citric acid, glucose, sucrose, lactose, maltose.
3. the anode material for lithium-ion batteries LiFePO for preparing according to claim 1 4method, it is characterized in that: the non-metallic vessel in described step (2), step (6) is silicon carbide crucible, graphite crucible or alumina crucible.
4. according to preparing anode material for lithium-ion batteries LiFePO described in claim 1-3 any one 4method, it is characterized in that: magnetic field intensity when described magnetic separation is 30-95KA/m.
CN201310029020.7A 2013-01-25 2013-01-25 Method for preparing cathode material-lithium iron phosphate of lithium ion battery by utilizing steel slag Expired - Fee Related CN103094579B (en)

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