CN112194182B - Preparation method of chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile - Google Patents
Preparation method of chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile Download PDFInfo
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Abstract
A preparation method of a chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile belongs to the technical field of lithium ion batteries. Aiming at the problems of slow electrode reaction kinetics, low first coulombic efficiency and specific capacity and the like of the traditional chromium oxide anode, the method comprises the following steps: preparing chromium oxide; preparing vulcanized polyacrylonitrile; preparing lithiation vulcanized polyacrylonitrile; and mixing the prepared lithiation vulcanized polyacrylonitrile and the chromium oxide, and performing ball milling at 200rpm for 1 hour to obtain the chromium oxide anode containing lithiation vulcanized polyacrylonitrile. The chromium oxide lithium ion battery anode material containing the lithiated vulcanized polyacrylonitrile has uniform particles, and has the advantages of remarkably improving the first coulombic efficiency, the reversible specific capacity and the conductivity; the lithium-containing vulcanized polyacrylonitrile can be used for modifying other electrode materials, and the organic carbon skeleton has higher conductivity, lithium supplement capacity and electrochemical reaction voltage platform, and can be popularized to other electrode material systems.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a chromium oxide lithium ion battery anode material containing lithium vulcanized polyacrylonitrile.
Background
With the continuous upgrading and upgrading of portable electronic devices and 3C digital products and the rapid development of new energy vehicles, the demand for batteries with high specific energy, high safety, high stability and low cost is continuously increasing. At present, layered positive electrode materials of high nickel oxides, such as LiNi0.8Co0.1Ni0.1O2And LiNi0.8Co0.15Ni0.05O2And the like, has higher reversible specific capacity, but the discharge specific capacity of the lithium ion battery is still lower than 230mAh g-1The requirement of the energy density of the single battery of 300-500Wh/kg is difficult to achieve. The method for developing the high-capacity lithium ion battery anode material is used for constructing a high-energy-density energy storage power supplyThe important route of (a). Multi-electron reacted chromium oxide CrOx(Cr8O21And Cr2O5Etc.), has higher theoretical specific mass capacity (over 580mAh/g), and is a ternary high nickel material LiNi0.8 Co0.1Mn0.1O2More than twice, and also has higher working voltage (3.0V, vs Li)+/Li), is a very promising lithium battery positive electrode material with both high specific capacity and high voltage. However, chromium oxide CrOxThe preparation process of (A) is immature, CrOxThe electrochemical performance (specific discharge capacity and cycle performance) of the lithium ion battery is greatly influenced by preparation conditions; second, CrOxThe lithium battery cathode material has large irreversible capacity loss for the first time, and the charge-discharge mechanism of the lithium battery cathode material is unclear.
Aiming at the problems of the chromium oxide, people mainly change the molecular and crystal structures of the chromium oxide by regulating and controlling the preparation conditions of materials such as pyrolysis temperature, pyrolysis time, heating rate and the like; alternatively, CrO can be suppressed by increasing the conductivity of the material by carbon coating or the like3Easily dissolved in an organic donor solvent. However, the method cannot essentially change the problems of low discharge specific capacity of the chromium oxide, slow electrode kinetic reaction, low first coulombic efficiency and the like. In actual testing, CrOxThe discharge specific capacity of the material is generally lower than 350mAh/g, the rate capability and the cycle performance of the battery are poor, and particularly the first coulombic efficiency is generally lower than 85%, so that the commercial application of the material is greatly hindered. A simple and efficient method is found, the first coulombic efficiency, the discharge specific capacity and the electrode process dynamics of the chromium oxide are improved, and the method has important significance for structure/mechanism exploration and commercial application of a high-capacity chromium oxide anode.
Disclosure of Invention
The invention provides a preparation method of a chromium oxide lithium ion battery anode material containing lithiation vulcanized polyacrylonitrile, aiming at the problems of slow electrode reaction kinetics, low first coulombic efficiency and specific capacity and the like of the traditional chromium oxide anode.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile comprises the following steps:
the method comprises the following steps: preparation of chromium oxide: placing chromium trioxide powder in a tubular furnace, calcining at high temperature in an oxidizing atmosphere, grinding, sieving, and washing with water to remove unreacted chromium trioxide to obtain chromium oxide;
step two: and (3) preparing vulcanized polyacrylonitrile: mixing polyacrylonitrile monomer and sublimed sulfur, and calcining for 1-20 hours at 250-350 ℃ in an argon environment to obtain vulcanized polyacrylonitrile;
step three: the preparation method of lithiation vulcanized polyacrylonitrile specifically comprises the following steps:
A. dissolving biphenyl in an ether solvent under the protection of Ar gas, stirring for 5-48 hours, adding lithium metal according to the mass ratio of the biphenyl to the lithium metal of 1:1, and stirring overnight to obtain a black and uniform Li-BP chemical pre-lithiation solution;
B. pouring the sulfurized polyacrylonitrile into the excessive Li-BP chemical pre-lithiation solution, and stirring for 5-48 hours;
C. centrifugally washing the reaction product by using DME, and drying the reaction product for 12 hours at 80 ℃ in Ar gas to obtain lithiated vulcanized polyacrylonitrile;
step four: and mixing the lithiated sulfurized polyacrylonitrile and the chromium oxide, and ball-milling at 200rpm for 1 hour to obtain the chromium oxide anode containing lithiated sulfurized polyacrylonitrile.
Compared with the prior art, the invention has the beneficial effects that:
(1) the chromium oxide lithium ion battery anode material containing the lithiated vulcanized polyacrylonitrile has uniform particles, and has the advantages of remarkably improving the first coulombic efficiency, the reversible specific capacity and the conductivity;
(2) the lithium-containing vulcanized polyacrylonitrile can be used for modifying other electrode materials, and the organic carbon framework has higher conductivity, lithium supplement capacity and electrochemical reaction voltage platform and can be popularized to other electrode material systems;
(3) the lithium-containing sulfurized polyacrylonitrile is prepared by a chemical method, is simple and quick, and can be popularized to the prelithiation of other sulfur-containing substances. The invention provides technical support for promoting commercialization of the high-energy density lithium ion battery.
Drawings
FIG. 1 is a three-electrode cyclic voltammogram of the chemical prelithiation solution of Li-BP/DME prepared in example 1; a working electrode: platinum, counter electrode: lithium sheet, reference electrode: lithium sheet, sweeping speed: 100 mV/s;
FIG. 2 is a first charge-discharge curve diagram of lithiated polyacrylonitrile sulfide prepared in example 1 in a range of 2.5-4.0V;
FIG. 3 shows chromium oxide (Cr) prepared in example 13O8) A charge-discharge curve graph of the anode material;
FIG. 4 is a graph of the lithiated sulfurized polyacrylonitrile-containing chromium oxide (Cr) prepared in example 13O8) And (3) a charge-discharge curve diagram of the lithium ion battery anode material.
Detailed Description
The technical solutions of the present invention are further described below by the description of the specific embodiments, but the present invention is not limited thereto, and modifications and equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit of the technical solutions of the present invention, and the technical solutions of the present invention are covered by the protection scope of the present invention.
The invention adopts a high-temperature calcination method to prepare high-valence chromium oxides with different components, then adopts a chemical method to prepare a lithium-containing sulfurized polyacrylonitrile material, and further carries out composite treatment on the chromium oxides and the lithium-containing sulfurized polyacrylonitrile to obtain the chromium oxide lithium ion battery anode material containing the lithium-containing sulfurized polyacrylonitrile. The lithium-containing vulcanized polyacrylonitrile can provide a platform with higher lithium supplement specific capacity and discharge voltage, and the organic carbon skeleton in the lithium-containing vulcanized polyacrylonitrile has higher conductivity, higher electrochemical stability and higher electrolyte compatibility; the lithium-containing vulcanized polyacrylonitrile has good reversibility and compatibility of an ester (ether) electrolyte system in a working range of 2.0-4.0V. Therefore, the prepared chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile has the advantages of obviously improved first coulombic efficiency, discharge voltage platform, reversible specific capacity, charge-discharge specific capacity and conductivity, and can provide technical support for commercial application of the chromium oxide anode.
The first embodiment is as follows: the embodiment describes a preparation method of a chromium oxide lithium ion battery cathode material containing lithiated vulcanized polyacrylonitrile, which specifically comprises the following steps:
the method comprises the following steps: preparation of chromium oxide: placing chromium trioxide powder in a tubular furnace, calcining at high temperature in an oxidizing atmosphere, grinding, sieving, and washing with water to remove unreacted chromium trioxide to obtain high-valence chromium oxide;
step two: and (3) preparing vulcanized polyacrylonitrile: mixing polyacrylonitrile monomer and sublimed sulfur, and calcining for 1-20 hours at 250-350 ℃ in an argon environment to obtain vulcanized polyacrylonitrile with different sulfur contents;
step three: the preparation method of lithiation vulcanized polyacrylonitrile specifically comprises the following steps:
A. dissolving Biphenyl (BP) in an ether solvent under the protection of Ar gas, stirring for 5-48 hours, adding lithium metal according to the mass ratio of the biphenyl to the lithium metal of 1:1, and stirring overnight to obtain a black and uniform Li-BP chemical pre-lithiation solution;
B. pouring the sulfurized polyacrylonitrile into the excessive Li-BP chemical pre-lithiation solution, and stirring for 5-48 hours;
C. carrying out centrifugal washing on the reaction product by using DME, and drying the reaction product for 12 hours at 80 ℃ in Ar gas to obtain lithiated vulcanized polyacrylonitrile, so as to realize the pre-lithiation treatment of sulfide;
step four: and mixing the prepared lithiation vulcanized polyacrylonitrile and the chromium oxide, ball-milling at 200rpm for 1 hour to obtain a chromium oxide anode containing lithiation vulcanized polyacrylonitrile, and testing electrochemical properties in different electrolyte systems. The test electrolyte comprises ester electrolyte and ether electrolyte and consists of different lithium salts and solvents.
The chromium oxide lithium ion battery anode containing lithiated vulcanized polyacrylonitrile has the advantages of obviously improved first coulombic efficiency, discharge specific capacity and conductivity. Lithiated polyacrylonitrile sulfide can provide a higher lithium supplement capacity and discharge voltage platform. The organic carbon skeleton in the lithiated sulfurized polyacrylonitrile can provide higher electric conductivity.
The second embodiment is as follows: in the first step of the preparation method of the chromium oxide lithium ion battery cathode material containing lithiated vulcanized polyacrylonitrile, the oxidizing atmosphere is air or oxygen.
The third concrete implementation mode: in the first step, the calcination temperature is 300-450 ℃, the time is 1-5 hours, and the heating rate is 1-10 ℃/min.
The fourth concrete implementation mode: in the second step of the preparation method of the lithium ion battery cathode material containing the lithium-transition polyacrylonitrile, the polyacrylonitrile monomer: the mass ratio of sublimed sulfur is 1: 1-10, and the sulfur content of the prepared vulcanized polyacrylonitrile is 30-60%.
The fifth concrete implementation mode: in the second step of the preparation method of the chromium oxide lithium ion battery cathode material containing lithiated vulcanized polyacrylonitrile, the calcining temperature is 300 ℃.
The sixth specific implementation mode: in the third step a, the ether solvent is one or more of ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
The seventh embodiment: in the third step a, the lithium metal is one or more of a lithium sheet, lithium powder, and a lithium block.
The specific implementation mode is eight: in the first specific embodiment, the preparation method of the chromium oxide lithium ion battery anode material containing lithiated sulfurized polyacrylonitrile comprises the following steps: the mass ratio of the chromium oxide is 0.05-0.5: 1.
example 1:
(1) 6.0g of chromium trioxide crystal powder is placed in a small porcelain boat and is pyrolyzed continuously for 2 hours in a tube furnace under the air atmosphere and at 350 ℃. Grinding and sieving the product, and washing with water to remove unreacted chromium trioxide to obtain high-valence chromium oxide (Cr)3O8)。
(2) 0.4g of polyacrylonitrile, 1.6g of sublimed sulfur and 10ml of absolute ethyl alcohol are put into a ball milling pot, and ball milling is carried out for 300min at the rotating speed of 500 rpm. And (3) after centrifugation, washing and drying, putting the sample in a tube furnace, calcining for 10 hours at 300 ℃ in an argon atmosphere, and preparing the vulcanized polyacrylonitrile material with the S content of about 43%.
(3) 1.54g of biphenyl powder is added into 10mL of ethylene glycol dimethyl ether solvent, stirred for 10 minutes, added with a lithium sheet according to the stoichiometric ratio of 1:1 and stirred for 12 hours to obtain a black uniform Li-BP/DME solution. Sulfurized polyacrylonitrile was added to the Li-BP/DME solution and stirred for 12 hours. After washing with DME for 3 times by centrifugation, the lithiated polyacrylonitrile was obtained by drying at 80 ℃ for 12 hours in an argon atmosphere.
(4) 0.1g of lithiated polyacrylonitrile sulfide and 0.4g of chromium oxide (Cr) prepared as described above3O8) And (5) placing the mixture into a ball milling tank, and carrying out ball milling for 2 hours at the rotating speed of 200rpm to prepare the chromium-containing vulcanized polyacrylonitrile composite anode. Mixing the active substance: super P: PVDF is mixed in a ratio of 8:1:1, and the mixture is pasted and prepared into a pole piece by using 1M LiPF6And preparing a CR 2032 button cell by taking the + EC/DMC (3:7) + FEC (5%) as electrolyte and the metallic lithium as a negative electrode, and testing the electrochemical performance, wherein the voltage interval is 2.0-4.5V.
As can be seen from the cyclic voltammogram shown in FIG. 1, the Li-BP/DME prelithiation solution in example 1- (3) has a pair of reversible redox peaks at 0.765V and 0.267V. It is understood from the first charge-discharge curve of lithiated polyacrylonitrile sulfide shown in fig. 2 that lithiated polyacrylonitrile sulfide has excellent irreversibility in the charge-discharge range of 2.5 to 4.0V. As shown in FIG. 3, chromium oxide (Cr)3O8) First discharge and charge specific capacity of positive electrode306.5mAh/g and 269.1mAh/g respectively, and the first coulombic efficiency is 87.8 percent; as shown in FIG. 4, chromium oxide (Cr) containing lithiated sulfurized polyacrylonitrile3O8) The first discharge and charge specific capacities of the lithium ion battery anode are 317.5mAh/g and 326.5mAh/g respectively, the first coulombic efficiency is 102.8%, the reversible specific capacity is improved, and the polarization of the battery is obviously reduced.
Example 2:
the difference between this example and example 1 is that the electrochemical behavior of the lithium ion battery cathode material of chromium oxide of lithiated polyacrylonitrile sulfide is studied by adjusting and controlling the components of chromium oxide. The preparation conditions of chromium oxide are regulated, and in the preparation process of chromium oxide, the synthesis conditions of calcining atmosphere (air or oxygen), calcining temperature, calcining time and heating rate are mainly changed, so that different chromium oxides, such as Cr5O13、Cr8O21、Cr2O5、Cr3O8、CrO2And the like.
Example 3:
this example differs from example 1 in that the sulfur content of the vulcanized polyacrylonitrile was adjusted. In the preparation of vulcanized polyacrylonitrile, by changing the monomer ratio of polyacrylonitrile: the feeding ratio of sublimed sulfur, the calcining temperature and the calcining time can change the sulfur content in the vulcanized polyacrylonitrile, and the percentage of the sulfur is usually 30-60%. The sulfur content in the sulfurized polyacrylonitrile can also affect the electrochemical properties such as the electric conductivity, the lithium supplement capacity and the like of the lithiated sulfurized polyacrylonitrile prepared subsequently.
Example 4:
the difference between this example and example 1 is that the preparation method of lithiated polyacrylonitrile sulfide was adjusted, and the types of the solvent and the metal lithium were adjusted when the lithium-biphenyl prelithiation solution was prepared. The invention adopts the chemical pre-lithiation method to treat the sulfurized polyacrylonitrile, generally uses an ether solvent which can be one or more of ethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether; the lithium metal used may be one or more of lithium flake, lithium block, lithium powder.
Example 5:
the difference between this example and example 1 is that the electrochemical behavior of the lithium ion battery cathode material of chromium oxide of lithiated sulfurized polyacrylonitrile was studied by changing the electrolyte composition. The electrolyte mainly comprises ester electrolyte and ether electrolyte. The lithium salt of the electrolyte includes various kinds including lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium dioxalate borate, lithium tetrafluoroborate, lithium difluorophosphate, and the like. The ester electrolyte solvent comprises one or more of ethylene carbonate, dimethyl carbonate, fluoroethylene carbonate, propylene carbonate, diethyl carbonate and the like. The ether electrolyte solvent comprises one or more of ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether and 1, 3-dioxolane.
Claims (8)
1. A preparation method of a chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile is characterized by comprising the following steps: the method specifically comprises the following steps:
the method comprises the following steps: preparation of chromium oxide: placing chromium trioxide powder in a tubular furnace, calcining at high temperature in an oxidizing atmosphere, grinding, sieving, and washing with water to remove unreacted chromium trioxide to obtain chromium oxide;
step two: preparing vulcanized polyacrylonitrile: mixing polyacrylonitrile monomer and sublimed sulfur, and calcining for 1-20 hours at 250-350 ℃ in an argon environment to obtain vulcanized polyacrylonitrile;
step three: the preparation method of lithiation vulcanized polyacrylonitrile comprises the following steps:
A. dissolving biphenyl in an ether solvent under the protection of Ar gas, stirring for 5-48 hours, adding lithium metal according to the mass ratio of the biphenyl to the lithium metal of 1:1, and stirring overnight to obtain a black and uniform Li-BP chemical pre-lithiation solution;
B. pouring the sulfurized polyacrylonitrile into the excessive Li-BP chemical pre-lithiation solution, and stirring for 5-48 hours;
C. centrifugally washing the reaction product by using DME, and drying the reaction product for 12 hours at 80 ℃ in Ar gas to obtain lithiated vulcanized polyacrylonitrile;
step four: and mixing the lithiated sulfurized polyacrylonitrile and the chromium oxide, and ball-milling at 200rpm for 1 hour to obtain the chromium oxide anode containing lithiated sulfurized polyacrylonitrile.
2. The preparation method of the chromium oxide lithium ion battery anode material containing lithium sulfide polyacrylonitrile as claimed in claim 1, characterized in that: in the first step, the oxidizing atmosphere is air or oxygen.
3. The preparation method of the chromium oxide lithium ion battery anode material containing lithium sulfide polyacrylonitrile as claimed in claim 1, characterized in that: in the first step, the calcination temperature is 300-450 ℃, the calcination time is 1-5 hours, and the heating rate is 1-10 ℃/min.
4. The preparation method of the chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile according to claim 1, characterized in that: in the second step, the polyacrylonitrile monomer: the mass ratio of sublimed sulfur is 1: 1-10, and the sulfur content of the prepared vulcanized polyacrylonitrile is 30-60%.
5. The preparation method of the chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile according to claim 1, characterized in that: in the second step, the temperature of the calcination is 300 ℃.
6. The preparation method of the chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile according to claim 1, characterized in that: in the third step A, the ether solvent is one or more of ethylene glycol dimethyl ether, triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
7. The preparation method of the chromium oxide lithium ion battery anode material containing lithiated vulcanized polyacrylonitrile according to claim 1, characterized in that: in the third step A, the lithium metal is one or more of lithium sheets, lithium powder and lithium blocks.
8. The preparation method of the chromium oxide lithium ion battery anode material containing lithium sulfide polyacrylonitrile as claimed in claim 1, characterized in that: in the fourth step, lithiation of sulfurized polyacrylonitrile: the mass ratio of the chromium oxide is 0.05-0.5: 1.
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