CN112542586B - Subcritical continuous synthesis method of lithium iron fluoride sulfate anode material - Google Patents

Subcritical continuous synthesis method of lithium iron fluoride sulfate anode material Download PDF

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CN112542586B
CN112542586B CN202011418127.7A CN202011418127A CN112542586B CN 112542586 B CN112542586 B CN 112542586B CN 202011418127 A CN202011418127 A CN 202011418127A CN 112542586 B CN112542586 B CN 112542586B
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汪伟伟
程蒙
杨茂萍
万宁
陈�峰
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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Abstract

The invention discloses a subcritical continuous synthesis method of a fluorinated lithium iron sulfate anode material, which relates to the technical field of lithium ion battery anode materials and comprises the following steps: selecting pickling waste liquor of a steel mill as a raw material, mixing high-temperature steel mill waste water with a high-temperature lithium source, sulfate and villiaumite solution under high pressure by utilizing the strong solubility and ion transfer capacity of subcritical water, and synthesizing nano LiFeSO in one step4And F, a positive electrode material. The invention has the beneficial effects that: the material obtained by the invention has the advantages of pure phase, good crystallinity, low cost, simple process, convenient regulation and control and easy large-scale continuous industrial production.

Description

Subcritical continuous synthesis method of lithium iron fluoride sulfate anode material
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a subcritical continuous synthesis method of a fluorinated lithium iron sulfate anode material.
Background
Since the 21 st century, the explosion of the population caused the exhaustion of traditional fossil energy and the serious destruction of ecological environment. China is the largest coal consuming country in the world, and the consumption of coal accounts for more than 70% of the total amount of commodity energy, so that the pollution of coal waste gas emission is a main source of air pollution in China. Therefore, the development of clean, low-cost green energy is an urgent problem.
Secondary lithium ion batteries, one of the representatives of green new energy, have outstanding advantages in terms of safety, life, and energy density. Compared with the traditional nickel-cadmium battery, the lithium ion battery has larger capacity, higher working voltage and long service life, can work in a wide temperature range of-20 to +55 ℃, and has the advantages of high safety, no memory effect, no pollution and the like. LiFeSO4The F anode material uses the Fe element with higher content, low cost and environmental friendliness in the earth crust as the core element for chemical energy storage, and the S and F elements required by synthesis are both low in price, so that the F anode material is low in costThis high-capacity positive electrode material. Triple-inclined phase LiFeSO4The F anode material has a three-dimensional ion migration channel, so that the F anode material has high ion mobility and excellent rate performance. The F ions have strong electronegativity, and are combined with metal ions together with sulfate radicals having an induction effect to form a firm three-dimensional framework structure, so that the LiFeSO4The F anode material has excellent cycle life and high safety, and is a secondary lithium ion battery material with high performance and low cost.
At present, the cost reduction of the lithium ion battery is the mainstream direction, the synthesis process is short, the parameter regulation and control are easy, the production efficiency is high, the quality is good and is more difficult, and the low-cost industrial waste liquid is not utilized to produce LiFeSO in the prior art4The invention provides a method for preparing a F anode material, which takes subcritical water as a reaction medium, and utilizes industrial waste liquid with ultralow cost to synthesize LiFeSO with low cost and high performance by a one-step liquid phase method4And F, a positive electrode material.
Disclosure of Invention
The technical problem to be solved by the invention is to adopt low-cost industrial waste liquid to continuously produce high-performance nano low-cost LiFeSO by one-step liquid phase synthesis4And F, a positive electrode material.
The invention solves the technical problems through the following technical means:
a subcritical continuous synthesis method of a fluorinated lithium iron sulfate anode material comprises the following steps:
(1) adding an impurity removing agent into the iron-smelting industrial pickling waste liquid, filtering, measuring the concentration of Fe ions in the waste liquid, then injecting the waste liquid into a raw material tank, heating to 140-;
(2) adding a lithium source, sulfate and villiaumite into the raw material tank in the step (1) under the condition of stirring;
(3) pumping reaction raw materials in a raw material tank into a reaction tank, keeping the temperature and the stirring speed of the reaction tank constant, keeping the pressure in the reaction tank at 3-5Mpa, opening a discharge valve of the reaction tank after the pressure reaches 50-70% of the total volume of the reaction tank, and allowing the reacted product to flow into a finished product tank # 1;
(4) filling a finished product tank #1, standing, then injecting supernatant suspension slurry of a finished product into a finished product tank #2, carrying out filter pressing on lower slurry in the finished product tank #1, washing for 3 times, and then drying;
(5) and carrying out heat treatment on the dried powder to obtain the lithium iron fluoride sulfate anode material.
Has the advantages that: the invention adopts the pickling waste liquor of the steel mill as the raw material, ensures that water is in a subcritical state, has strong reaction activity, utilizes the strong solubility and the ion migration capability of subcritical water, mixes the high-temperature steel mill wastewater with the high-temperature lithium source, sulfate and villiaumite solution under high pressure, and synthesizes the nano LiFeSO by one step4And F, a positive electrode material.
The material obtained by the invention has the advantages of pure phase, good crystallinity, low cost, simple process, convenient regulation and control and easy large-scale continuous industrial production.
The temperature of the raw material tank is adjusted, which is beneficial to the nucleation of the reaction and controls the appearance, the particle size distribution and the purity of the product.
Preferably, the impurity removing agent in the step (1) is Na2CO3、NaHCO3、K2CO3The ratio of the addition amount of the impurity removing agent to the mass of the waste liquid is 0.01-0.2: 1; the reducing agent is one or a mixture of more of ascorbic acid, citric acid and aniline, and the mass ratio of the addition amount of the reducing agent to Fe ions is 0.2-0.8: 1.
Preferably, after the iron-smelting industrial pickling waste liquid in the step (1) is subjected to impurity removal and filtration, the molar ratio of the total molar amount of Cr, Ni and Cu in the waste liquid to the molar amount of Fe is not more than 0.01: 1.
Preferably, the lithium source in the step (2) is one or a mixture of several of lithium hydroxide, lithium acetate and lithium nitrate, and the molar weight ratio of the lithium source to the Fe ions is 1-3: 1; the sulfate is one or a mixture of more of sodium sulfate, potassium sulfate and ammonium sulfate, and the molar weight ratio of the sulfate to Fe ions is 2-8: 1; the fluorine salt is one or a mixture of more of ammonium fluoride, lithium fluoride and sodium fluoride, and the molar weight ratio of the fluorine salt to the Fe ions is 1-2: 1.
Has the advantages that: under the above reaction conditions, the generation of a hetero phase can be reduced.
Preferably, the temperature of the raw material tank in the step (2) is 140-200 ℃.
Preferably, the temperature of the reaction tank in the step (3) is 150-.
Has the advantages that: reaction conditions in the reaction tank outside the above range are extremely likely to cause the production of a hetero phase.
Preferably, the standing time in the step (4) is 8-12 h.
Preferably, the washing liquid used for washing in the step (4) is deionized water or 0.01mol/L LiOH solution.
Preferably, the heat treatment temperature in the step (5) is 400-.
The invention has the advantages that:
(1) the invention uses subcritical water as a reaction medium, utilizes industrial waste liquid with ultralow cost, and synthesizes LiFeSO with low cost and high performance by one-step liquid phase4And F, a positive electrode material.
(2) According to the invention, other elements such as Cr and the like can be further extracted from the clear suspension slurry in the finished product tank #2 after synthesis, so that the production cost is further reduced.
(3) The subcritical liquid phase synthesis can obtain nano-sized high-performance LiFeSO4The discharge specific capacity of the F anode material under the 1C multiplying power is up to 144mAh/g, and the material is short in synthesis process, easy in parameter regulation and control and high in production efficiency.
(4) Compared with the template method, the method can reduce the influence of different templates on the material performance.
Drawings
FIG. 1 shows LiFeSO obtained in example 1 of the present invention4Scanning electron microscope image of the F material;
FIG. 2 shows LiFeSO obtained in example 1 of the present invention41C rate cycle performance diagram of F material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The subcritical continuous synthesis method of the fluorinated lithium iron sulfate cathode material comprises the following steps of:
(1) adding Na with the mass of 1 percent into the pickling waste liquid in the iron (steel) smelting industry2CO3Impurity removing agent, filtering the waste liquid, testing the concentrations of Cr, Ni, Cu and Fe ions by adopting an inductively coupled plasma emission spectrometer (ICP-OES), wherein the molar ratio of the total molar amount of the Cr, Ni and Cu elements to the molar amount of the Fe elements is less than or equal to 0.01, then injecting the waste liquid into a No. 1 raw material tank, heating to 200 ℃, and adding ascorbic acid with the molar amount of Fe being 0.2 time as a reducing agent; wherein the Fe ion is the sum of ferrous ion and ferric ion;
(2) according to the Fe ion: lithium hydroxide: sodium sulfate: ammonium fluoride is 1: 1: 2:1, respectively preparing solutions of a lithium source, sulfate and a villaumite solution, and then respectively injecting the solutions into a raw material tank to heat to 200 ℃;
(3) pumping the solution in the raw material tank into a reaction tank by using a precision pump, controlling the temperature and the pressure of the reaction tank to be 220 ℃ and 5MPa, controlling the stirring speed to be 500rpm, and opening a discharge valve to allow the reacted product to flow into a finished product tank #1 when the volume of the reaction tank reaches 70 percent of the volume;
(4) after filling the finished product tank #1, standing for 8h, injecting supernatant suspension slurry in the finished product tank #1 into the finished product tank #2, filter-pressing the lower slurry in the finished product tank #1, washing for 3 times by using 0.01mol/L LiOH solution, and then drying; other elements such as Cr and the like can be further extracted from the clear suspension slurry in the finished product tank #2, so that the production cost is further reduced;
(5) carrying out heat treatment on the dried powder for 5h at 800 ℃ in a high-purity nitrogen atmosphere to obtain highly-crystallized LiFeSO4And F, a positive electrode material. In this example, the purity of the high-purity nitrogen is more than or equal to 99.999%.
FIG. 1 is a scanning electron microscope image of the product of this embodiment, from which LiFeSO can be seen4The F material is a nano-scale bulk particle with a short ion diffusion path. FIG. 2 is a graph of the product of this example showing 1C rate cycling performance, the first discharge specific capacity of the material is 144mAh/g, and the 100-cycle specific capacity is maintained at 95%.
Example 2
The subcritical continuous synthesis method of the fluorinated lithium iron sulfate cathode material comprises the following steps of:
(1) adding Na with the mass of 4 percent into the pickling waste liquid in the iron (steel) smelting industry2CO33% NaHCO33% of K2CO3As a composite impurity removing agent, after the waste liquid is filtered, an inductively coupled plasma emission spectrometer ICP-OES is adopted to test the concentrations of Cr, Ni, Cu and Fe ions, wherein the molar ratio of the total molar amount of the Cr, Ni and Cu elements to the molar amount of the Fe element is less than or equal to 0.01, then the waste liquid is injected into a No. 1 raw material tank to be heated to 140 ℃, and ascorbic acid with the molar amount of Fe being 0.4 time and citric acid with the molar amount of Fe being 0.4 time are added as reducing agents; wherein the Fe ion is the sum of ferrous ion and ferric ion;
(2) according to the Fe ion: lithium hydroxide: sodium sulfate: ammonium fluoride is 1: 3: 8: 2, respectively preparing solutions of a lithium source, sulfate and a villaumite solution, and then respectively injecting the solutions into a raw material tank to heat to 140 ℃;
(3) pumping the solution in the raw material tank into a reaction tank by using a precision pump, controlling the temperature and the pressure of the reaction tank to be 150 ℃ and 3MPa, controlling the stirring speed to be 100rpm, and opening a discharge valve to allow the reacted product to flow into a finished product tank #1 when the volume of the reaction tank reaches 50% of the volume;
(4) after filling the finished product tank #1, standing for 12h, injecting supernatant suspension slurry in the finished product tank #1 into the finished product tank #2, filter-pressing the lower slurry in the finished product tank #1, washing for 3 times by using 0.01mol/L LiOH solution, and then drying; other elements such as Cr and the like can be further extracted from the clear suspension slurry in the finished product tank #2, so that the production cost is further reduced;
(5) carrying out heat treatment on the dried powder for 20h at 400 ℃ in a high-purity nitrogen atmosphere to obtain highly-crystallized LiFeSO4And F, a positive electrode material.
The 1C rate first discharge specific capacity of the product of the embodiment is 142mAh/g, and the 100-cycle specific capacity retention rate is 93%.
Example 3
The subcritical continuous synthesis method of the fluorinated lithium iron sulfate cathode material comprises the following steps of:
(1) NaHCO with the mass of 2 percent is added into the pickling waste liquid in the iron (steel) smelting industry3And 1% of K2CO3As a composite impurity removing agent, after the waste liquid is filtered, an inductively coupled plasma emission spectrometer ICP-OES is adopted to test the concentrations of Cr, Ni, Cu and Fe ions, wherein the molar ratio of the total molar amount of the Cr, Ni and Cu elements to the molar amount of the Fe element is less than or equal to 0.01, then the waste liquid is injected into a No. 1 raw material tank to be heated to 180 ℃, and aniline with the molar amount of 0.6 time of that of the Fe is added as a reducing agent; wherein the Fe ion is the sum of ferrous ion and ferric ion;
(2) according to the Fe ion: lithium hydroxide: sodium sulfate: ammonium fluoride is 1: 2: 6: 2, respectively preparing solutions of a lithium source, sulfate and a villaumite solution, and then respectively injecting the solutions into a raw material tank to heat to 180 ℃;
(3) pumping the solution in the raw material tank into a reaction tank by using a precision pump, controlling the temperature and the pressure of the reaction tank to be 170 ℃ and 3.5MPa, controlling the stirring speed to be 250rpm, and opening a discharge valve to allow the reacted product to flow into a finished product tank #1 when the volume of the reaction tank reaches 65 percent of the volume;
(4) after filling the finished product tank #1, standing for 10h, injecting supernatant suspension slurry in the finished product tank #1 into the finished product tank #2, filter-pressing the lower slurry in the finished product tank #1, washing for 3 times by using 0.01mol/L LiOH solution, and then drying; other elements such as Cr and the like can be further extracted from the clear suspension slurry in the finished product tank #2, so that the production cost is further reduced;
(5) drying the powder in high purityHeat treating at 600 deg.c for 10 hr in nitrogen atmosphere to obtain highly crystallized LiFeSO4And F, a positive electrode material.
The 1C rate first discharge specific capacity of the product of the embodiment is 146mAh/g, and the 100-cycle specific capacity retention rate is 90%.
Example 4
The subcritical continuous synthesis method of the fluorinated lithium iron sulfate cathode material comprises the following steps of:
(1) NaHCO with the mass of 2 percent is added into the pickling waste liquid in the iron (steel) smelting industry3And 1% of K2CO3As a composite impurity removing agent, after the waste liquid is filtered, an inductively coupled plasma emission spectrometer ICP-OES is adopted to test the concentrations of Cr, Ni, Cu and Fe ions, wherein the molar ratio of the total molar amount of the Cr, Ni and Cu elements to the molar amount of the Fe element is less than or equal to 0.01, then the waste liquid is injected into a No. 1 raw material tank to be heated to 180 ℃, and citric acid with the molar amount of Fe being 0.1 time, ascorbic acid with the molar amount of Fe being 0.1 time and aniline with the molar amount of Fe being 0.1 time are added to serve as reducing agents; wherein the Fe ion is the sum of ferrous ion and ferric ion;
(2) according to the Fe ion: lithium hydroxide: sodium sulfate: ammonium fluoride is 1: 1: 4: 1.5, respectively preparing solutions of a lithium source, sulfate and a villaumite solution, and then respectively injecting the solutions into a raw material tank to heat to 200 ℃;
(3) pumping the solution in the raw material tank into a reaction tank by using a precision pump, controlling the temperature and the pressure of the reaction tank to be 180 ℃ and 4MPa, controlling the stirring speed to be 4100rpm, and opening a discharge valve to allow the reacted product to flow into a finished product tank #1 when the volume of the reaction tank reaches 55 percent of the volume;
(4) after filling the finished product tank #1, standing for 9h, injecting supernatant suspended slurry in the finished product tank #1 into the finished product tank #2, filter-pressing the lower slurry in the finished product tank #1, washing for 3 times by using 0.01mol/L LiOH solution, and then drying; other elements such as Cr and the like can be further extracted from the clear suspension slurry in the finished product tank #2, so that the production cost is further reduced;
(5) the dried powder is subjected to heat treatment for 150 hours at 500 ℃ in a high-purity nitrogen atmosphere to obtain highly-crystallized LiFeSO4And F, a positive electrode material.
The 1C rate first discharge specific capacity of the product of the embodiment is 140mAh/g, and the 100-cycle specific capacity retention rate is 91%.
Example 5
(1) Adding 4% K by mass into the pickling waste liquid in iron (steel) smelting industry2CO3As a composite impurity removing agent, after the waste liquid is filtered, an inductively coupled plasma emission spectrometer ICP-OES is adopted to test the concentrations of Cr, Ni, Cu and Fe ions, wherein the molar ratio of the total molar amount of the Cr, Ni and Cu elements to the molar amount of the Fe element is less than or equal to 0.01, then the waste liquid is injected into a No. 1 raw material tank, the temperature is raised to 170 ℃, and citric acid with the molar amount of 0.25 time that of the Fe is added as a reducing agent; wherein the Fe ion is the sum of ferrous ion and ferric ion;
(2) according to the Fe ion: lithium hydroxide: sodium sulfate: ammonium fluoride is 1: 2.5: 5: 1, respectively preparing solutions of a lithium source, sulfate and a villaumite solution, and then respectively injecting the solutions into a raw material tank to be heated to 155 ℃;
(3) pumping the solution in the raw material tank into a reaction tank by using a precision pump, controlling the temperature and the pressure of the reaction tank to be 190 ℃ and 3MPa, controlling the stirring speed to be 300rpm, and opening a discharge valve to allow the reacted product to flow into a finished product tank #1 when the volume of the reaction tank reaches 68 percent of the volume;
(4) after filling the finished product tank #1, standing for 10h, injecting supernatant suspended slurry in the finished product tank #1 into the finished product tank #2, filter-pressing the lower slurry in the finished product tank #1, washing the lower slurry for 3 times by using deionized water, and then drying the lower slurry; other elements such as Cr and the like can be further extracted from the clear suspension slurry in the finished product tank #2, so that the production cost is further reduced;
(5) carrying out heat treatment on the dried powder for 8h at 700 ℃ in a high-purity nitrogen atmosphere to obtain highly-crystallized LiFeSO4And F, a positive electrode material.
The 1C rate first discharge specific capacity of the product of the embodiment is 138mAh/g, and the 100-cycle specific capacity retention rate is 96%.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. A subcritical continuous synthesis method of a fluorinated lithium iron sulfate anode material is characterized in that: the method comprises the following steps:
(1) adding an impurity removing agent into the iron-smelting industrial pickling waste liquid, filtering, measuring the concentration of Fe ions in the waste liquid, wherein the molar ratio of the total molar amount of Cr, Ni and Cu in the waste liquid to the molar amount of Fe is less than or equal to 0.01:1, then injecting the waste liquid into a raw material tank, heating to 140-;
(2) adding a lithium source, sulfate and villiaumite into the raw material tank in the step (1) under the condition of stirring;
(3) pumping reaction raw materials in a raw material tank into a reaction tank, keeping the temperature and the stirring speed of the reaction tank constant, keeping the pressure in the reaction tank at 3-5Mpa, opening a discharge valve of the reaction tank after the pressure reaches 50-70% of the total volume of the reaction tank, and allowing the reacted product to flow into a finished product tank # 1;
(4) filling a finished product tank #1, standing, then injecting supernatant suspension slurry of a finished product into a finished product tank #2, carrying out filter pressing on lower slurry in the finished product tank #1, washing for 3 times, and then drying;
(5) and carrying out heat treatment on the dried powder to obtain the lithium iron fluoride sulfate anode material.
2. The subcritical continuous synthesis method for a fluorinated lithium iron sulfate positive electrode material according to claim 1, characterized in that: the impurity removing agent in the step (1) is Na2CO3、NaHCO3、K2CO3The mass ratio of the added amount of the impurity removing agent to the waste liquid is 0.01-0.2: 1; the reducing agent is one or a mixture of more of ascorbic acid, citric acid and aniline, and the mass ratio of the addition amount of the reducing agent to Fe ions is 0.2-0.8: 1.
3. The subcritical continuous synthesis method for a fluorinated lithium iron sulfate positive electrode material according to claim 1, characterized in that: the lithium source in the step (2) is one or a mixture of more of lithium hydroxide, lithium acetate and lithium nitrate, and the molar weight ratio of the lithium source to Fe ions is 1-3: 1; the sulfate is one or a mixture of more of sodium sulfate, potassium sulfate and ammonium sulfate, and the molar weight ratio of the sulfate to Fe ions is 2-8: 1; the fluorine salt is one or a mixture of more of ammonium fluoride, lithium fluoride and sodium fluoride, and the molar weight ratio of the fluorine salt to the Fe ions is 1-2: 1.
4. The subcritical continuous synthesis method for a fluorinated lithium iron sulfate positive electrode material according to claim 1, characterized in that: the temperature of the raw material tank in the step (2) is 140-200 ℃.
5. The subcritical continuous synthesis method for a fluorinated lithium iron sulfate positive electrode material according to claim 1, characterized in that: the temperature of the reaction tank in the step (3) is 150-220 ℃, and the stirring speed is 100-500 rpm.
6. The subcritical continuous synthesis method for a fluorinated lithium iron sulfate positive electrode material according to claim 1, characterized in that: and (4) standing for 8-12 h.
7. The subcritical continuous synthesis method for a fluorinated lithium iron sulfate positive electrode material according to claim 1, characterized in that: and (4) washing liquid used for washing in the step (4) is deionized water or 0.01mol/L LiOH solution.
8. The subcritical continuous synthesis method for a fluorinated lithium iron sulfate positive electrode material according to claim 1, characterized in that: the heat treatment temperature in the step (5) is 400-800 ℃, the heat treatment time is 5-20h, and the atmosphere is high-purity nitrogen.
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