CN101948379B - Method for preparing battery-level ferrous oxalate - Google Patents
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Abstract
The invention provides a method for preparing battery-level ferrous oxalate, which is characterized in that high molecular weight water soluble polymer is added to a precursor for preparing the ferrous oxalate to form a complex compound structure or other structures with the precursor in order to prepare the battery-level ferrous oxalate by reacting with a precipitator. The preparation method of the precursor ferrisulphas comprises the following steps: ferrisulphas, the by-product of titanium dioxide is dissolved; then reduced iron powder is added to the dissolved ferrisulphas; and finally, the mixture is filtrated. In the invention, the high molecular weight water soluble polymer is introduced in the reaction process to suppress grain diameter of the ferrous oxalate; as a result, superfine ferrous oxalate with a uniform grain diameter is obtained. In addition, the method of the invention has the characteristics of sufficient raw materials, simple technical process, good and stable product quality, low cost and the like, and provides a new means of recycling the waste of the ferrisulphas.
Description
Technical field
The present invention relates to the energy storage material technical field, specifically refer to a kind of auxiliary method for preparing battery level iron oxalate of high molecular weight water-soluble polymer of utilizing.
Background technology
Along with the worsening shortages of chemical fuel source in the global range, force people to seek novel alternative clean energy.Lithium ion battery has the energy density height, output rating is large, average output voltage is high, self-discharge is little, but the memory-less effect fast charging and discharging, cycle performance is superior and the characteristics such as non-environmental-pollution, become the first choice of current portable type electronic product rechargeable, be considered to the most promising chemical power source.In lithium ion battery, positive electrode material is in occupation of center-stage, and the performance quality of positive electrode material has directly determined the property indices of final lithium cell product.Traditional positive electrode material mainly contains three kinds of cobalt acid lithium, lithium manganate and ternary materials.The cobalt acid lithium LiCoO of laminate structure
2Poor stability, explosive in the time of 150 ℃, cost is high, and only the price of cobalt contains the LiCoO of Co 60 % with regard to about 500,000 yuan/tons
2Surpass 400,000 yuan/tons, cycle life is short.And the lithium manganate LiMn of spinel structure
2O
4Although LiCoO is compared in security
2Good a lot, but the cycle life of hot environment is relatively poor, only about 500 times.
Along with the Recent Progresses In The Development of people to lithium ion anode material, it is found that iron lithium phosphate LiFePO
4In lithium ion have the reversibility that embeds/deviate from, can be used as the positive electrode material of lithium ion battery.While LiFePO
4Stability Analysis of Structures, security, high warm nature and thermostability obviously be better than other known positive electrode material.In addition, LiFePO
4Also have excellent cycle performance, but repeated charge reach more than 1000 times, and nontoxic, cheap, be real green material.So LiFePO
4Being considered to is optimal power vehicle lithium electricity positive electrode material at present.Because LiFePO
4The huge applications prospect and the economic benefit that have plurality of advantages and may bring since being found to be used to the positive electrode material of lithium cell, have caused rapidly great research boom, become a kind of novel material that causes the revolution of lithium ion battery industry.
At present; the large-scale production of ferric phosphate lithium cell is being carried out in high gear, and its application is very extensive, such as energy storage device, power tool, electromobile, electric bicycle etc.; market outlook are very huge, thereby lithium iron phosphate positive material is synthetic most important.The synthetic method of iron lithium phosphate mainly contains Ferrox route, tertiary iron phosphate route, ferric oxide route at present.Wherein the Ferrox route is take Ferrox as raw material, and the iron lithium phosphate of production has that performance is good, low cost and other advantages.This route occupies more than 60% of the total share in world market at present.
Ferrox is as one of starting material of synthesizing lithium ion battery anode active compound lithium iron phosphate, and its purity and particle diameter have important impact to the performance of iron lithium phosphate.The preparation method of prior art mesoxalic acid ferrous iron mixes divalent iron salt dissolving and oxalic acid or oxalate solution, realizes control to Ferrox particle diameter and crystal habit by the processing parameter of control building-up process.Chinese patent CN 1948259A discloses the production method of the special-purpose Ferrox of a kind of phosphoric acid (Asia) iron lithium, the method is take ferrous sulfate and oxalic acid as raw material, and to have prepared granularity be the monocline of 10-20 micron or tiltedly side or three oblique iron oxalate crystals by ferrous sulfate being carried out after the pre-treatment mixing solutions reaction with oxalic acid and ammonium oxalate.Although the method can access the Ferrox of different crystal forms but particle diameter is larger, be the 10-20 micron.In addition, Chinese patent CN101058536A and 200910304079.6 etc. discloses equally and has adopted ferrous sulfate to produce the method for Ferrox, but there are problems in the Ferrox that adopts above synthetic method to obtain, or foreign matter content is high, or synthetic Ferrox particle diameter is large, and the performance of iron lithium phosphate is comprised the impact that the generations such as stability of chemical property and product are difficult to expect.Therefore the performance of Ferrox directly has influence on further developing of LiFePO 4 material industrialization.But technology mesoxalic acid ferrous iron awaits further to improve in the performance aspect purity and the granularity at present.
Summary of the invention
Technical problem to be solved in the utility model is the preparation method that the battery level iron oxalate that a kind of granularity is little and even, purity is high is provided for the present situation of prior art.
Foreign ion exists in the Ferrox kind and content are very large to the performance impact of synthetic product iron lithium phosphate, so the purity of Ferrox is most important to the performance of iron lithium phosphate; On the other hand for iron lithium phosphate, because its electronics, ionic conductivity are low, just have preferably chemical property and processing characteristics when needing its median size to be the 1-5 micron, therefore also stricter to the requirement of raw material particle size, usually need raw material particle size less than 10 microns, adopting the little Ferrox of particle diameter is raw material, can effectively control the particle diameter of iron lithium phosphate, also can improve homogeneity and the reactivity of batch mixing simultaneously.Therefore needing the Ferrox of production high purity, small particle size to satisfy the demand of iron lithium phosphate, also is the developing direction of battery level iron oxalate simultaneously.
It is to be that the present invention solves the problems of the technologies described above the technical scheme of taking: the water-soluble polymer that adds high molecular in the precursor of preparation Ferrox, form complex structure with described precursor, and then prepare battery level iron oxalate by the reaction with precipitation agent.Adopt the auxiliary preparation of the water-soluble polymer Ferrox of this type of high molecular to have two aspect effects, this family macromolecule and precursor form complex structure on the one hand, can reduce the speed of reaction with precipitation agent; Increase on the other hand the viscosity of solution, in the process of growth of Ferrox crystal grain, hinder or limit the migration of iron ion and oxalate denominationby, suppress the growth of Ferrox crystal grain; Ferrox crystal grain mobile that the initial stage of also having limited simultaneously forms assembles, and greatly reduces little crystal grain and assembles and form oarse-grained probability, finally can obtain particle diameter little, be evenly distributed and battery level iron oxalate product that purity is high.
Concrete preparation method is as follows:
The preparation method of battery level iron oxalate is characterized in that adding the water-soluble polymer of high molecular in the precursor of preparation Ferrox, strong stirring mixes it, and stir speed (S.S.) can be controlled at 400-1000rpm; Add the precipitation agent reaction behind the regulator solution PH and be precipitated thing, this throw out filtering drying is namely obtained Ferrox; Preferably, the temperature of reaction behind the adding precipitation agent can be 0-90 ℃, and the reaction times is 0.5-3 hour.
Wherein said water-soluble polymer is selected from one or more in polyacrylamide 10000000, PEG20000, PEG 20000, polyvinyl alcohol 2499, polyvinyl alcohol 1788, polyvinyl alcohol 1750 and the PVP K-90, and the add-on of water-soluble polymer is the 0.001-5% of described precursor weight;
Described precipitation agent is selected from one or several in oxalic acid, ammonium oxalate, sodium oxalate, potassium oxalate and the lithium oxalate, and the consumption of precipitation agent is 0.6～1 of described precursor molar weight.
Preferably, described precursor is ferrous sulfate, the preparation method of described ferrous sulfate be with the by-product ferrous sulfate during of titanium dioxide through dissolving, add reduced iron powder and ammoniacal liquor by removing by filter sandstone and the resulting copperas solution of other heavy metal ion.Described solution PH is between the 1-6.
When being controlled at 0.1-1%, the addition of the water-soluble polymer of described high molecular can obtain better effect; It is better that reaction times in above-mentioned each scheme is controlled at 0.5 hour resulting product property.
Compared with prior art, the invention provides the auxiliary method for preparing battery level iron oxalate of a kind of high molecular weight water-soluble polymer, obtained that purity is high, particle diameter is little and uniform Ferrox product, solved Ferrox and be difficult to greatly the shortcoming that mixes as particle diameter in the iron lithium phosphate raw material building-up process, to iron lithium phosphate chemical property and the stability of product played vital role.In addition, the present invention utilizes byproduct ferrous sulfate of titanium dioxide to be raw material, has eliminated the pollution of ferrous sulfate waste to environment, has also improved the added value of ferrous sulfate product; Used high molecular weight water-soluble polymer addition is little, has effectively reduced the raw materials cost of lithium ion battery anode material lithium iron phosphate.Preparation method of the present invention is easy, easy to operate, is applicable to scale operation.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the embodiment of the invention 1 prepared battery level iron oxalate.
Fig. 2 is the scanning electron microscope (SEM) photograph of the embodiment of the invention 1 prepared battery level iron oxalate under high-amplification-factor.
A is the Granularity Distribution curve of battery level iron oxalate prepared in the embodiment of the invention 1 among Fig. 3;
B is the size distribution curve of the prepared battery level iron oxalate of Comparative Examples of the present invention among Fig. 3;
Fig. 4 is the scanning electron microscope (SEM) photograph of the prepared battery level iron oxalate of Comparative Examples of the present invention;
Fig. 5 is the scanning electron microscope (SEM) photograph of the prepared battery level iron oxalate of Comparative Examples under high-amplification-factor among the present invention.
Embodiment
Embodiment is described in further detail the utility model below in conjunction with accompanying drawing.
2 kilograms of byproduct ferrous sulfate of titanium dioxide are dissolved in 4 liters of deionized waters, under the stir speed (S.S.) of 600rpm, add reduced iron powder 20 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=3, heating systems and to keep temperature be 30 ℃, in ferrous sulfate filtrate, add PEG 20000 solution 1200 grams that concentration is 1.5wt%, adding rapidly concentration after stirring 10 minutes under the stir speed (S.S.) of 600rpm is 50wt% oxalic acid solution 1100 grams, 30 ℃ of insulations 30 minutes, generate faint yellow Ferrox crystalline deposit after reinforced the finishing.To make battery level iron oxalate after precipitated product filtration, washing, the oven dry.The purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.5%, and median size is 4.2 microns.Be the scanning electron microscope (SEM) photograph of prepared battery level iron oxalate as illustrated in fig. 1 and 2.Fig. 3 A is the size distribution curve of prepared battery level iron oxalate.
Embodiment 2
1 kilogram of byproduct ferrous sulfate of titanium dioxide is dissolved in 3 liters of deionized waters, under the stir speed (S.S.) of 500rpm, add reduced iron powder 10 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=1, heating systems and to keep temperature be 60 ℃, in ferrous sulfate filtrate, add PEG20000 solution 200 grams that concentration is 3wt%, adding rapidly concentration after stirring 10 minutes under the stir speed (S.S.) of 500rpm is 50% ammonium oxalate solution, 970 grams, insulation is 2 hours after reinforced the finishing, generate faint yellow Ferrox crystallization, then with the product filtration washing, oven dry makes battery level iron oxalate, the purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.6%, and median size is 4.8 microns.
Embodiment 3
2 kilograms of byproduct ferrous sulfate of titanium dioxide are dissolved in 4 liters of deionized waters, under the stir speed (S.S.) of 800rpm, add reduced iron powder 20 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=2, keeping system temperature is 10 ℃, in ferrous sulfate filtrate, add polyacrylamide 10000000 solution 1000 grams that concentration is 0.5wt%, adding rapidly concentration after stirring 10 minutes under the stir speed (S.S.) of 800rpm is 50% sodium oxalate solution, 1500 grams, after reinforced the finishing system was kept 2.5 hours under 10 ℃ of conditions, generate faint yellow Ferrox crystallization, then with the product filtration washing, oven dry makes battery level iron oxalate, the purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.5%, and median size is 3.4 microns.
Embodiment 4
2 kilograms of byproduct ferrous sulfate of titanium dioxide are dissolved in 4 liters of deionized waters, under the stir speed (S.S.) of 1000rpm, add reduced iron powder 20 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=4, making system keep temperature is 0 ℃, in ferrous sulfate filtrate, add PVP K-90 solution 100 grams that concentration is 10wt%, adding rapidly concentration after stirring 10 minutes under the stir speed (S.S.) of 1000rpm is 50% Potassium Oxalate Solution, 1800 grams, after reinforced the finishing system was kept 2 hours under 0 ℃ of condition, generate faint yellow Ferrox crystallization, then with the product filtration washing, oven dry makes battery level iron oxalate, the purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.7%, and median size is 2.6 microns.
Embodiment 5
1 kilogram of byproduct ferrous sulfate of titanium dioxide is dissolved in 3 liters of deionized waters, under the stir speed (S.S.) of 700rpm, add reduced iron powder 10 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=6, keeping system temperature is 20 ℃, in ferrous sulfate filtrate, add polyvinyl alcohol 2499 solution 200 grams that concentration is 5wt%, adding rapidly concentration after stirring 10 minutes under the stir speed (S.S.) of 700rpm is 50% lithium oxalate solution, 600 grams, after reinforced the finishing system was kept 3 hours under 20 ℃ of conditions, generate faint yellow Ferrox crystallization, then with the product filtration washing, oven dry makes battery level iron oxalate, the purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.6%, and median size is 3.2 microns.
Embodiment 6
2 kilograms of byproduct ferrous sulfate of titanium dioxide are dissolved in 4 liters of deionized waters, under the stir speed (S.S.) of 600rpm, add reduced iron powder 20 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=5, heating systems and to keep temperature be 50 ℃, in ferrous sulfate filtrate, add polyvinyl alcohol 2499 and PEG 20000 (both weight ratios are 1: 1) mixing solutions 800 grams that concentration is 5wt%, adding rapidly concentration after under the stir speed (S.S.) of 1000rpm 10 minutes is 50% oxalic acid and sodium oxalate (both weight ratios are 1: 1) mixing solutions 1500 grams, insulation is 3 hours after reinforced the finishing, generate faint yellow Ferrox crystallization, then with the product filtration washing, oven dry makes battery level iron oxalate, the purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.5%, and median size is 4.3 microns.
Embodiment 7
1 kilogram of byproduct ferrous sulfate of titanium dioxide is dissolved in 3 liters of deionized waters, under the stir speed (S.S.) of 400rpm, add reduced iron powder 10 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=2.5, heating systems and to keep temperature be 90 ℃, in ferrous sulfate filtrate, add polyvinyl alcohol 1788 and PVP K-90 (both weight ratios are 1: 2) solution 1000 grams that concentration is 5wt%, adding rapidly concentration after stirring 10 minutes under the stir speed (S.S.) of 800rpm is 50% oxalic acid and potassium oxalate (both weight ratios are 1: 1) mixing solutions 850 grams, insulation is 30 minutes after reinforced the finishing, generate faint yellow Ferrox crystallization, then with the product filtration washing, oven dry makes battery level iron oxalate, the purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.5%, and median size is 4.8 microns.
Embodiment 8
2 kilograms of byproduct ferrous sulfate of titanium dioxide are dissolved in 4 liters of deionized waters, under the stir speed (S.S.) of 900rpm, add reduced iron powder 20 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=3.5, heating systems and to keep temperature be 80 ℃, in ferrous sulfate filtrate, add polyacrylamide 10000000 and PEG 20000 (both weight ratios are 1: 40) mixing solutions 1000 grams that concentration is 8wt%, adding rapidly concentration after stirring 10 minutes under the stir speed (S.S.) of 900rpm is 50% ammonium oxalate and sodium oxalate (both weight ratios are 1: 1) mixing solutions 1600 grams, insulation is 1 hour after reinforced the finishing, generate faint yellow Ferrox crystallization, then with the product filtration washing, oven dry makes battery level iron oxalate, the purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.5%, and median size is 4.7 microns.
Embodiment 9
2 kilograms of byproduct ferrous sulfate of titanium dioxide are dissolved in 4 liters of deionized waters, under the stir speed (S.S.) of 400rpm, add reduced iron powder 20 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=1.5, heating systems and to keep temperature be 70 ℃, add concentration in the ferrous sulfate filtrate and be 6% polyvinyl alcohol 1750 solution 1000 grams, adding rapidly concentration after stirring 10 minutes under the stir speed (S.S.) of 800rpm is 50% ammonium oxalate and sodium oxalate (both weight ratios are 1: 1) mixing solutions 1500 grams, insulation is 1.5 hours after reinforced the finishing, generate faint yellow Ferrox crystallization, then with the product filtration washing, oven dry makes battery level iron oxalate, the purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.5%, and median size is 4.6 microns.
Comparative Examples
2 kilograms of byproduct ferrous sulfate of titanium dioxide are dissolved in 4 liters of deionized waters, under the stir speed (S.S.) of 600rpm, add reduced iron powder 20 grams, after heating 3 hours under 50 ℃ of conditions, filter the transparent filtrate of ferrous sulfate after being purified, regulate this pH value of solution=3, heating systems and to keep temperature be 30 ℃, then adding rapidly concentration is 50wt% oxalic acid solution 1100 grams, 30 ℃ of insulations 30 minutes, generates faint yellow Ferrox crystalline deposit after reinforced the finishing.To make the battery level iron oxalate product after precipitated product filtration, washing, the oven dry.The purity that obtains battery level iron oxalate through the test of Xray fluorescence spectrometer and laser particle analyzer is 99.5%, and median size is 11.7 microns (Fig. 3 B).Be depicted as the scanning electron microscope (SEM) photograph of prepared battery level iron oxalate such as Figure 4 and 5.
Claims (8)
1. the preparation method of a battery level iron oxalate, it is characterized in that in the precursor of preparation Ferrox, adding the water-soluble polymer of high molecular, strong stirring mixes it, add the precipitation agent reaction behind the regulator solution Ph and be precipitated thing, this throw out filtering drying is namely obtained Ferrox;
Wherein said water-soluble polymer is selected from one or more in polyacrylamide 10000000, PEG20000, PEG 20000, polyvinyl alcohol 2499, polyvinyl alcohol 1788, polyvinyl alcohol 1750 and the PVP K-90, and the add-on of water-soluble polymer is the 0.001-5% of described precursor weight;
Described precipitation agent is oxalic acid and sodium oxalate or oxalic acid and potassium oxalate, and the consumption of precipitation agent is 0.6～1 of described precursor molar weight.
2. the preparation method of battery level iron oxalate according to claim 1, it is characterized in that described precursor is ferrous sulfate, the preparation method of described ferrous sulfate be with the by-product ferrous sulfate during of titanium dioxide through dissolving, add reduced iron powder and ammoniacal liquor by removing by filter sandstone and the resulting copperas solution of other heavy metal ion.
3. the preparation method of battery level iron oxalate according to claim 1, the temperature of reaction that it is characterized in that adding behind the precipitation agent is 0-90 ℃, the reaction times is 0.5-3 hour.
4. the preparation method of battery level iron oxalate according to claim 1, the speed that it is characterized in that described strong stirring is 400-1000rpm.
5. the preparation method of battery level iron oxalate according to claim 1 is characterized in that described solution PH is between the 1-6.
6. the preparation method of the battery level iron oxalate when described to 4 arbitrary claims according to claim 1, the addition that it is characterized in that described water-soluble polymer is 0.1-1%.
7. the preparation method of the battery level iron oxalate when described to 4 arbitrary claims according to claim 1 is characterized in that the described reaction times is 0.5 hour.
8. the preparation method of the battery level iron oxalate when described according to claim 6 is characterized in that the described reaction times is 0.5 hour.
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Families Citing this family (6)
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| CN102557916B (en) * | 2011-12-02 | 2014-11-05 | 江西赣锋锂业股份有限公司 | Preparation method of special battery-grade ferrous oxalate for lithium iron phosphate |
| CN103408417A (en) * | 2013-07-18 | 2013-11-27 | 合肥亚龙化工有限责任公司 | Preparation method for nanoscale ferrous oxalate |
| CN104617290B (en) * | 2013-11-04 | 2017-02-08 | 中国科学院大连化学物理研究所 | Homogenous precipitation method for preparing Fe2O3 nanobelt and Fe2O3 nanobelt-carbon composite material |
| CN105732359B (en) * | 2016-04-18 | 2017-11-28 | 昆明理工大学 | A kind of method that battery level iron oxalate is prepared using iron and steel pickling waste liquid |
| CN106356532B (en) * | 2016-10-19 | 2018-09-28 | 山东三秋新能源科技有限公司 | A kind of production technology of nanoscale anhydrous oxalic acid ferrous iron |
| CN107863530B (en) * | 2017-11-03 | 2020-04-28 | 山东科技大学 | Method for preparing high-density lithium iron phosphate by adopting siderite |
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