CN113060715B - Method for synthesizing lithium ferric manganese phosphate cathode material - Google Patents
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to the technical field of lithium ion batteries, and provides a method for synthesizing a novel lithium ferric manganese phosphate anode material, which comprises the following steps: s1, putting manganese dioxide, phosphoric acid and water into a container, stirring, adding aniline, and continuously stirring to obtain polyaniline; s2, weighing an iron source, a lithium source, a carbon source and an organic auxiliary agent, adding into polyaniline, and grinding and stirring; s3, drying and calcining in an air atmosphere to obtain a precursor; s4, adding a carbon source into the precursor again, adding a grinding medium, and grinding to obtain grinding slurry; s5, drying the grinding slurry in vacuum to obtain reaction powder; and S6, sintering the reaction powder under the protective atmosphere, cooling to room temperature, crushing, and sieving to obtain the polyaniline/carbon-coated lithium manganese iron phosphate battery anode material. Through the technical scheme, the problems of low discharge capacity ratio and poor circulation stability in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a synthesis method of a novel lithium manganese iron phosphate cathode material.
Background
Recently, ternary positive electrode materials (LiNiCoMnO) 2 ) The advantages of high discharge capacity, high specific energy of weight and volume, good environmental protection, low toxicity and the like become hot spots in the current industry and application. It combines LiCoO 2 Has excellent cycle performance of LiNiO 2 And a high discharge capacity of LiMnO, and 2 excellent safety performance, and becomes the lithium ion battery anode material for the high energy density hybrid electric vehicle. The biggest problem of the ternary material is easy oxygen evolution, causing combustion and explosion of the battery system. As the production of electric vehicles increases and the phenomena of explosion and ignition become more and more, people begin to use ternary materials with caution.
Lithium iron phosphate materials were discovered in 1997, and lithium ion batteries made from lithium iron phosphate have the advantages of excellent safety, cost, resource, and cycle performance, and are the hot spot of current research. The method has wide application prospect in the aspects of large-scale electric vehicles, energy storage power stations, military use and the like. The main defects of the lithium iron phosphate anode are that the platform voltage is only 3.2V, and the voltage is about 30% lower than the voltage of 3.7V of the ternary material, lithium cobaltate and lithium manganate. This results in a reduced specific energy and increased cost for the battery system. How to increase the system voltage of the phosphate positive electrode material becomes one of the main research hotspots in academia and industry.
Experiments show that after manganese ions are doped into lithium iron phosphate, the voltage discharge platform of the lithium ion battery can reach about 4V, and the median discharge voltage can be increased to 3.7-3.8V, which is equivalent to that of a ternary cathode material. However, the current lithium iron manganese phosphate cathode material has very low ionic conductivity and electronic conductivity, so that the capacity of the material is difficult to exert, part of manganese ions are subjected to disproportionation reaction and dissolved in an electrolyte, so that the cycle performance of the material is poor, and the material is difficult to process due to high specific surface area.
The traditional material system is synthesized by generally adopting manganese carbonate, ferrous oxalate, lithium carbonate and the like as raw materials, the processing difficulty of the materials is high, particularly, the materials are easy to deteriorate in the grinding process, the viscosity of slurry is greatly increased, the grinding efficiency is reduced, so that the microcosmic components of the materials are uneven, and the electrochemical performance of the materials is poor. In addition, the carbon micropore effect causes larger specific surface area, and brings certain difficulty to the subsequent processing and coating process.
The polyaniline conductive polymer is a good conductive agent material, has good conductivity, good lithium ion transmission performance and unique and excellent cross-linked network structure, and has important significance for improving battery capacity exertion, high-rate charge and discharge, cycle performance and the like. However, (NH) is often used in practical production and application of polyaniline 4 ) 2 S 2 O 8 The lithium iron phosphate is simply coated by initiating polymerization, and excessive impurities brought by the polymerization cause adverse side reactions to the cyclic charge and discharge of the anode material, so that the capacity exertion of the battery cell is influenced, and the service life of the battery is shortened. On the other hand, polyaniline having a general modification effect generally acts to enhance the conductive effect of lithium manganese iron phosphate, and does not sufficiently cooperate to exhibit the conductive effect.In addition, the lithium iron phosphate material is simply coated, and the lithium iron manganese phosphate has inconsistent particle size and uneven size distribution, so that the conductive effect of the anode material is not uniform, and local failure is easily caused after multiple cycles.
Disclosure of Invention
The invention provides a synthesis method of a novel lithium ferric manganese phosphate anode material, which solves the problems of low discharge capacity ratio and poor cycle stability in the prior art.
The technical scheme of the invention is as follows:
a method for synthesizing a novel lithium ferric manganese phosphate anode material comprises the following steps:
s1, placing manganese dioxide, phosphoric acid and water in a container, stirring for 2 to 4h, adding aniline, and continuously stirring for 1 to 2h to obtain polyaniline;
s2, weighing an iron source, a lithium source, a carbon source and an organic auxiliary agent, adding into polyaniline, and grinding and stirring for 4 to 12h;
s3, drying and calcining in an air atmosphere to obtain a precursor;
s4, adding a carbon source into the precursor again, adding a grinding medium, and grinding to obtain grinding slurry;
s5, drying the grinding slurry in vacuum to obtain reaction powder;
and S6, sintering the reaction powder under the protective atmosphere, cooling to room temperature, crushing, and sieving to obtain the polyaniline/carbon-coated lithium manganese iron phosphate battery anode material.
As a further technical scheme, the lithium source is lithium carbonate or lithium hydroxide, the iron source is one or more of ferrous oxalate, ferric oxide and ferric carbonate, and the carbon source is one or more of glucose, sucrose, polyethylene glycol and phenolic resin.
As a further technical scheme, the molecular formula of the lithium iron manganese phosphate battery positive electrode material is LiMn x Fe y PO 4 /PAn, wherein the value of x is 0.4 to 0.8, the value of y is 0.2 to 0.6, and x + y =1.
As a further technical scheme, the organic auxiliary agent comprises hydroxyalkyl hydroxypolymethylene ether, N-palmitoyl hydroxyproline cetyl ester and polyvinylpyrrolidone, and the mass ratio of the hydroxyalkyl hydroxypolymethylene ether to the N-palmitoyl hydroxyproline cetyl ester to the polyvinylpyrrolidone is (0.5 to 0.7): (0.2 to 0.3): 1, the organic auxiliary agent accounts for 20-30% of the mass of the iron source.
As a further technical scheme, the total weight ratio of the grinding medium to the reaction materials is (1 to 10): 1.
as a further technical scheme, the grinding medium is one or more of water, ethanol or methanol.
As a further technical scheme, the protective atmosphere is nitrogen or ammonia decomposition gas atmosphere.
As a further technical scheme, the mass ratio of the iron source to the lithium source to the carbon source is as follows: 1: (1 to 1.55): (1.86 to 2.32).
As a further technical scheme, in the step S3, the calcining temperature is 300 to 800 ℃, and the calcining time is 2 to 10 hours; in the step S5, the vacuum drying temperature is 100 to 120 ℃, and the mixture is dried for 6 to 12h under the vacuum condition of 0.01 MPa; in the step S6, the sintering temperature is 600 to 900 ℃, and the sintering time is 6 to 48h.
As a further technical scheme, the ratio of the mass/g of manganese dioxide to the volume/ml of phosphoric acid is (1: (1 to 1.12), wherein the mass concentration of the phosphoric acid is 85%, and the volume ratio of the phosphoric acid to the aniline is 1: (1 to 1.4).
The working principle and the beneficial effects of the invention are as follows:
1. the invention takes a lithium source, an iron source, a manganese source and a phosphorus source as raw materials, and is prepared by a solid-phase reaction method, conductive polymer polyaniline (PAn) is also added into the raw materials to carry out subsequent coating modification on the lithium manganese iron phosphate anode material, and the lithium manganese iron phosphate anode material is uniformly coated by the polymer conductive polyaniline material, so that the phosphate anode material with high sphericity, uniform components, higher voltage and stable cycle performance is conveniently and rapidly synthesized. The coating of the polyaniline effectively stabilizes the structure of the material, inhibits the material and the electrolyte from generating side reaction, improves the electrochemical performance of the anode material by utilizing the rapid ionic/electronic conductivity of the polyaniline, and simultaneously avoids the direct contact of the lithium ferric manganese phosphate electrolyte and the reduction of the dissolution of Mn ions caused by the corrosion of the electrolyte. And on the other hand, polyaniline is used for coating to replace the traditional carbon coating, so that the problem that the large specific surface area is difficult due to carbon micropores in the processing process is solved.
2. The invention obtains polyaniline by initiating polymerization of manganese dioxide under acid condition, and simultaneously, the manganese dioxide can be directly used as a raw material for preparing lithium manganese iron phosphate, thereby avoiding using the traditional (NH) 4 ) 2 S 2 O 8 Excessive impurities brought by the initiation of polymerization coating bring adverse side reactions to the cyclic charge and discharge of the anode material, thereby influencing the capacity exertion of the battery core and shortening the service life of the battery; and the lithium manganese iron phosphate is combined with a plurality of point line surfaces of the polyaniline on a framework formed by carbon to form an interactively communicated conductive network, so that the electron conduction and the transmission and diffusion of lithium ions are promoted, and the rate capability and the cycle performance of the lithium manganese iron phosphate are improved.
3. According to the invention, when the polyaniline is used for coating the anode material, an organic auxiliary agent is added, wherein polyvinylpyrrolidone is used as a surfactant, hydroxyalkyl hydroxypolymethylene ether and N-palmitoyl hydroxyproline cetyl ester are used as dispersants, so that the lithium iron manganese phosphate has consistent particle size and uniform size distribution, the coating capability of the polyaniline on the lithium iron manganese phosphate anode material is improved, and the cycle performance and the stability of the lithium ion battery are further improved.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a schematic structural diagram of a button cell;
in the figure, 1 is a copper mold, 2 is electrolyte, 3 is a stainless steel gasket, 4 is a lithium sheet, 5 is a diaphragm, 6 is a button battery shell, 7 is a positive electrode material wafer, and 8 is a spring.
Fig. 2 is a discharge curve diagram of a battery fabricated from the cathode material synthesized in example 1 of the present invention.
Fig. 3 is a discharge curve diagram of a battery prepared from the cathode material synthesized in example 2 of the present invention.
Fig. 4 is a discharge curve diagram of a battery prepared from the cathode material synthesized in example 3 of the present invention.
Fig. 5 is a discharge curve of a battery fabricated from the synthesized cathode material of comparative example 3 according to the present invention.
Detailed Description
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 only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
Example 1
60.9g of analytically pure manganese dioxide, 68ml of 85% phosphoric acid and 302ml of deionized water are placed in a container and continuously stirred for 4 hours, then 93ml of aniline is added, and stirring is continued for 2 hours to obtain the polyaniline. 24g of ferric oxide, 37g of lithium carbonate, 22.3g of glucose monohydrate, 1.1g of hydroxyalkyl hydroxypolymethylene ether, 0.5g of cetyl N-palmitoyl hydroxyproline and 2.1g of polyvinylpyrrolidone were weighed and added to the polyaniline solution, and the mixture was ground and stirred for 12 hours. And then drying in an air atmosphere, and calcining in the air atmosphere at 800 ℃ for 10 hours to obtain the precursor.
Adding 22.3g of monohydrate glucose into the precursor again, adding 100g of water serving as a grinding medium, and putting the mixture into a high-speed ball mill for grinding for 8 hours to obtain grinding slurry with the particle size D50 of 0.85 um.
And (3) putting the ground slurry into a rake type vacuum drier, and drying for 12 hours at 100 ℃ under the vacuum of 0.01MPa to obtain reaction powder.
And (3) putting the reaction powder into an electric furnace protected by nitrogen atmosphere for sintering at 600 ℃ for 48 hours, and discharging the reaction powder after cooling to room temperature. Further crushing and sieving to obtain a finished product of the cathode material, and identifying the finished product as LiMn 0.7 Fe 0.3 PO 4 a/PAn material.
Example 2
60.9g of analytically pure manganese dioxide, 68ml of 85% phosphoric acid and 302ml of deionized water are placed in a container and continuously stirred for 3 hours, then 93ml of aniline is added, and stirring is continued for 1 hour to obtain the polyaniline. 24g of ferric oxide, 24g of lithium hydroxide, 22.3g of glucose monohydrate, 1.6g of hydroxyalkyl hydroxypolymethylene ether, 0.7g of cetyl N-palmitoyl hydroxyproline and 2.4g of polyvinylpyrrolidone are weighed and added into the polyaniline liquid, and grinding and stirring are carried out for 8 hours. And then drying in an air atmosphere, and calcining in the air atmosphere at the calcining temperature of 500 ℃ for 8 hours to obtain the precursor.
Adding 22.3g of monohydrate glucose into the precursor again, adding 100g of water serving as a grinding medium, and putting the mixture into a high-speed ball mill for grinding for 8 hours to obtain grinding slurry with the particle size D50 of 0.85 mu m.
And (3) putting the ground slurry into a rake vacuum drier, and drying for 10 hours at 150 ℃ under the vacuum of 0.01MPa to obtain reaction powder.
And putting the reaction powder into an electric furnace protected by nitrogen atmosphere for sintering at 700 ℃ for 24 hours, and discharging the reaction powder after cooling to room temperature. And further crushing and sieving to obtain the polyaniline/carbon-coated lithium iron manganese phosphate battery anode material.
Example 3
60.98g of analytically pure manganese dioxide, 68ml of 85% phosphoric acid and 302ml of deionized water are placed in a container and continuously stirred for 2 hours, then 93ml of aniline is added, and stirring is continued for 1 hour to obtain polyaniline. 24g of ferric oxide, 24g of lithium hydroxide, 38.5g of sucrose, 1.4g of hydroxyalkyl hydroxypolymethylene ether, 0.7g of cetyl N-palmitoyl hydroxyproline and 2.3g of polyvinylpyrrolidone are weighed and added into the polyaniline liquid, and grinding and stirring are carried out for 10 hours. And then drying in an air atmosphere, and calcining in the air atmosphere at the calcining temperature of 600 ℃ for 6h to obtain the precursor.
And adding 38.5g of sucrose into the precursor again, adding 100g of water serving as a grinding medium, and putting the mixture into a high-speed ball mill for grinding for 8 hours to obtain grinding slurry with the particle size D50 of 0.85 um.
And (3) putting the ground slurry into a rake vacuum drier, and drying for 8 hours at the temperature of 120 ℃ under the vacuum of 0.01MPa to obtain dry reaction powder.
And putting the reaction powder into an electric furnace protected by nitrogen atmosphere for sintering at 650 ℃ for 36 hours, and discharging after cooling to room temperature. And further crushing and sieving to obtain the polyaniline/carbon-coated lithium iron manganese phosphate battery anode material.
Comparative example 1
The difference from example 2 is that hydroxyalkyl hydroxypolymethylene ether, cetyl N-palmitoyl hydroxyproline ester, and polyvinylpyrrolidone are not added, and the other steps are the same as example 2.
Comparative example 2
The difference from example 2 was that the hydroxyalkyl hydroxypolymethylene ether and cetyl N-palmitoyl hydroxyproline were not added, and the other examples were the same as example 2.
Comparative example 3
The process is the same as in example 2 except that polyvinylpyrrolidone is not added in example 2.
Comparative example 4
The difference from example 2 is that the hydroxyalkyl hydroxypolymethylene ether was not added, and the other examples are the same as example 2.
The cathode materials of the examples and comparative examples were made into button cells, lithium sheets were used as counter electrodes, and the fabrication of the electrodes and the assembly of the button cells are described below:
manufacturing electrodes and assembling button cells:
a. manufacture of positive pole piece
Weighing active substance lithium ferric manganese phosphate and conductive agent acetylene black according to the mass ratio of 16 to 3, putting the weighed materials into a small beaker with the volume of 50 mL, adding a proper amount of absolute ethyl alcohol to immerse the powder materials, and placing the powder materials in an ultrasonic dispersion instrument for ultrasonic treatment for 15 min. Stirring continuously in the ultrasonic process to uniformly mix the raw materials, and then taking out and dropwise adding a proper amount of PTFE (active substance: PTFE mass ratio 16. Stirring into a dough, and repeatedly rolling into a film with the thickness of about 0.14 mm by using a film pressing machine. And (3) drying the pressed film for 40 min at 80 ℃ in a vacuum drying oven, then poking a wafer with the diameter of about 1 cm by using a film poking device, weighing, putting into a vacuum glove box filled with argon for 4h, and assembling into the button cell.
b. Button cell assembly
Assembling the button cell in a vacuum glove box filled with argon atmosphere, taking the prepared membrane as a positive electrode, adopting a metal lithium sheet as a counter electrode, adopting a Celgard2400 microporous polypropylene membrane as a diaphragm, adopting 1 mol.L-1 LiPF6 dimethyl carbonate (DMC) + Ethylene Carbonate (EC) + Ethyl Methyl Carbonate (EMC) (1, vol) as an electrolyte, assembling the components into a CR2032 type button cell, putting the assembled button cell into a copper mold, screwing and sealing, and taking the assembled button cell as a measurement monomer to perform electrochemical test. Fig. 1 is a schematic structural diagram of a button cell.
Measurement of Charge and discharge Properties
In the experiment, the LAND CT2001A battery test system is used for testing the multiplying power and the cycle performance of the button battery. The temperature has a great influence on the electrochemical performance of the battery, and the test environment temperature of the battery is strictly controlled to be 25 +/-1 ℃. The test voltage range was 2.5 to 4.3V (vs. Li/Li +). The specific test regime is as follows:
(1) Standing for 1 min;
(2) Charging with constant current until the voltage is more than or equal to 4.3V;
(3) Charging at constant voltage for 15 min;
(4) Standing for 1 min;
(5) Discharging with constant current until the voltage is less than or equal to 2.5V;
(6) And (4) measuring the cycle performance, and repeating the steps.
TABLE 1 specific discharge capacity and cycling stability data for examples and comparative examples
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Specific discharge capacity/ |
160 | 159 | 151 | 135 | 138 | 143 | 140 |
| Capacity retention/% cycled 1000 times | 97.5 | 97 | 96 | 88 | 90 | 90.5 | 90.5 |
FIGS. 2 to 4 are discharge curves of batteries prepared from the positive electrode materials synthesized in examples 1 to 3 of the present invention, and the discharge capacity of the material at 0.2C is 160mAh g as shown in FIG. 2 -1 And two discharge voltage platforms, which are near 4.0V and near 3.5V respectively, correspond to the discharge platforms of manganese and iron respectively. Shows that the invention successfully synthesizes LiMn with good performance 0.7 Fe 0.3 PO 4 a/PAn material. The batteries prepared in comparative examples 1 to 4 are poor in discharge capacity and cycling stability because no organic auxiliary agent is addedIs poor. Also, it is noted that in comparative examples 2 to 4, when only one or two of hydroxyalkyl hydroxypolymethylene ether, cetyl N-palmitoyl hydroxyproline, and polyvinylpyrrolidone were added, there were limitations in the stability of the prepared battery and the degree of improvement in discharge capacity, and as shown in FIG. 5, the discharge capacity of comparative example 3 was only 143mAh g -1 And only by compounding the three components and adding the components into the slurry, the optimal stabilizing effect can be achieved.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing a lithium ferric manganese phosphate positive electrode material is characterized by comprising the following steps:
s1, putting manganese dioxide, phosphoric acid and water into a container, stirring, adding aniline, and continuously stirring to obtain polyaniline;
s2, weighing an iron source, a lithium source, a carbon source and an organic auxiliary agent, adding into polyaniline, and grinding and stirring;
s3, drying and calcining in an air atmosphere to obtain a precursor;
s4, adding a carbon source into the precursor again, adding a grinding medium, and grinding to obtain grinding slurry;
s5, drying the grinding slurry in vacuum to obtain reaction powder;
s6, sintering the reaction powder under the protective atmosphere, cooling to room temperature, crushing and sieving to obtain a polyaniline/carbon-coated lithium manganese iron phosphate battery positive electrode material;
the organic auxiliary agent comprises hydroxyalkyl hydroxy dimer linoleyl ether, N-palmitoyl hydroxyproline cetyl ester and polyvinylpyrrolidone.
2. The method for synthesizing a lithium ferric manganese phosphate positive electrode material according to claim 1, wherein the lithium source is lithium carbonate or lithium hydroxide, the iron source is one or more of ferrous oxalate, ferric oxide and ferric carbonate, and the carbon source is one or more of glucose, sucrose, polyethylene glycol and phenolic resin.
3. The method for synthesizing the lithium ferric manganese phosphate positive electrode material according to claim 1, wherein the molecular formula of the lithium ferric manganese phosphate positive electrode material is LiMn x Fe y PO 4 /PAn, wherein the value of x is 0.4 to 0.8, the value of y is 0.2 to 0.6, and x + y =1.
4. The method for synthesizing lithium ferric manganese phosphate cathode material according to claim 1, wherein the mass ratio of the hydroxyalkyl hydroxypolymethylene ether, the cetyl N-palmitoyl hydroxyproline and the polyvinylpyrrolidone is (0.5-0.7): (0.2-0.3): 1, the organic auxiliary agent accounts for 20-30% of the mass of the iron source.
5. The method for synthesizing the lithium ferric manganese phosphate cathode material according to claim 1, wherein the total mass ratio of the grinding medium to the reaction material is (1-10): 1.
6. the method for synthesizing the lithium ferric manganese phosphate cathode material according to claim 1, wherein the grinding medium is one or more of water, ethanol or methanol.
7. The method for synthesizing the lithium ferric manganese phosphate cathode material according to claim 1, wherein the protective atmosphere is nitrogen or ammonia decomposition gas atmosphere.
8. The method for synthesizing the lithium ferric manganese phosphate cathode material according to claim 2, wherein the mass ratio of the iron source to the lithium source to the carbon source is as follows: 1: (1 to 1.55): (1.86 to 2.32).
9. The method for synthesizing the lithium manganese iron phosphate cathode material according to claim 1, wherein in the step S3, the calcination temperature is 300 to 800 ℃, and the calcination time is 2 to 10 hours; in the step S5, the vacuum drying temperature is 100 to 120 ℃, and the mixture is dried for 6 to 12h under the vacuum condition of 0.01 MPa; in the step S6, the sintering temperature is 600 to 900 ℃, and the sintering time is 6 to 48h.
10. The method for synthesizing the lithium ferric manganese phosphate cathode material according to claim 1, wherein the ratio of mass/g of manganese dioxide to volume/ml of phosphoric acid is 1: (1-1.12), wherein the mass concentration of the phosphoric acid is 85%, and the volume ratio of the phosphoric acid to the aniline is 1: (1 to 1.4).
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