CN112670486B - Modified lithium titanate electrode material and preparation method thereof - Google Patents
Modified lithium titanate electrode material and preparation method thereof Download PDFInfo
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Abstract
The present invention belongs to the field of energy source and new material technology. The invention provides a preparation method of a modified lithium titanate electrode material, which is characterized in that phenolic resin and lithium dihydrogen phosphate are used as raw materials, a wet chemical method is adopted, the surface of lithium titanate with submicron size is coated with a mixture of the phenolic resin and the lithium dihydrogen phosphate, and then the surface of the lithium titanate is coated with a mixture of a graphitized carbon layer and the lithium phosphate through an inert atmosphere calcination treatment way. The preparation method provided by the invention has the advantages of cheap and easily available raw materials, simple and convenient wet chemical method and heat treatment method and process, low cost and suitability for large-scale production. The invention also provides the modified lithium titanate electrode material, the graphitized carbon layer and the lithium phosphate can both play a role in shielding the catalytic active sites on the surface of lithium titanate, and the synergistic benefit can be exerted, so that the rapid charge-discharge performance of the lithium titanate is improved, and the gas production behavior of the lithium titanate is inhibited.
Description
Technical Field
The invention relates to the technical field of energy and new materials, in particular to a modified lithium titanate electrode material and a preparation method thereof.
Background
Spinel type lithium titanate (Li)4Ti5O12LTO) has the characteristics of long cycle life, high safety performance, environmental friendliness and the like as a lithium ion battery cathode material, is considered to be one of the most promising power lithium ion battery cathode materials, and thus has attracted extensive attention. LTO has two distinct advantages over other anode materials: (1) the charging and discharging voltage platform is 1.55V (vs. Li +/Li), the reduction and decomposition of the common electrolyte on the surface can be avoided, and the safety is high; (2) the electrode material is 'zero strain' electrode material, the unit cell has almost no volume change in the process of lithium ion de-intercalation, and the cycle performance is excellent. However, LTO has low electronic conductivity and low lithium ion mobility, and the electrode polarization is severe during large current charging and discharging, resulting in poor rate performance.
In addition, in the practical use process, the LTO serving as the lithium ion battery negative electrode material has the problem of gas expansion. There are several known causes of battery gassing in which LTO is the negative electrode. Novak et al [ J.electrochem.Soc,2015,162(6): A870-A876; j.electrochem. Soc,2012,159(8) A1165-A1170] considers that moisture is introduced in the battery assembly process, so that the flatulence behavior of the LTO negative electrode material is caused by the decomposition of water in the charging and discharging processes; wu et al [ J.Power Sources,2013,237: 285-; he [ J.Power Sources,2012,202:253- ] 261; rep,2012,201:253-261] it is believed that the main cause of LTO gassing is gas generation due to the presence of catalytically active sites on the surface and interfacial reaction with the electrolyte. Practical application shows that the charged soft package battery with LTO as the negative electrode also has gas production behavior in a storage state, so that the existence of interface reaction between LTO and electrolyte is considered to be more convincing to cause gas expansion.
However, in the prior art, the surface modification of LTO is mostly limited to use of a single material, such as coating the surface of a carbon film or coating other inert materials, so that the improvement of LTO performance is limited.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a modified lithium titanate electrode material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a modified lithium titanate electrode material, which comprises the following steps:
(1) mixing lithium dihydrogen phosphate, phenolic resin and a solvent to obtain a suspension;
(2) mixing the suspension and lithium titanate, evaporating to dryness and grinding to obtain powder;
(3) and carrying out heat treatment on the powder in an inert atmosphere to obtain the modified lithium titanate electrode material.
Preferably, the mass ratio of the lithium dihydrogen phosphate to the phenolic resin in the step (1) is 1-10: 1 to 10.
Preferably, the solid content of the suspension in the step (1) is 0.1-1 g/L.
Preferably, the solvent in step (1) is alcohol or an alcohol aqueous solution.
Preferably, the mass ratio of the lithium titanate to the lithium dihydrogen phosphate to the phenolic resin in the step (2) is 94-99: 1-6;
the particle size of the lithium titanate is 100 nm-1 mu m.
Preferably, the mixing mode in the step (2) is mechanical stirring, the rotating speed of the mechanical stirring is 400-500 rpm, and the time of the mechanical stirring is 3-5 h.
Preferably, the temperature for evaporating in the step (2) is 50-70 ℃.
Preferably, the rotation speed of the grinding in the step (2) is 50-70 rpm, and the grinding time is 2-3 h.
Preferably, the temperature of the heat treatment in the step (3) is 700-800 ℃, and the time of the heat treatment is 1.5-2.5 h.
The invention also provides a modified lithium titanate electrode material obtained by the preparation method.
The invention provides a preparation method of a modified lithium titanate electrode material, which is characterized in that phenolic resin and lithium dihydrogen phosphate are used as raw materials, a wet chemical method is adopted, the surface of lithium titanate with submicron size is coated with a mixture of the phenolic resin and the lithium dihydrogen phosphate, and then the surface of the lithium titanate is coated with a mixture of a graphitized carbon layer and the lithium phosphate through an inert atmosphere calcination treatment way. The preparation method provided by the invention has the advantages of cheap and easily available raw materials, simple and convenient wet chemical method and heat treatment method and process, low cost and suitability for large-scale production.
The invention also provides the modified lithium titanate electrode material, and in the electrode material provided by the invention, the phosphate has a catalytic effect, so that the phenolic resin forms a graphitized carbon layer in the pyrolysis process. The graphitized carbon layer is beneficial to improving the electronic conductivity of lithium titanate, the lithium phosphate is beneficial to improving the lithium ion diffusion efficiency of lithium titanate, and in addition, the graphitized carbon layer and the lithium phosphate can both play a role in shielding the catalytic active sites on the surface of lithium titanate. The graphitized carbon layer and the lithium phosphate can exert synergistic benefits, namely the rapid charge and discharge performance of the lithium titanate is improved, and the gas production behavior of the lithium titanate is inhibited.
Drawings
Fig. 1 is an SEM image of a modified lithium titanate electrode material of example 1;
fig. 2 is a TEM image of a modified lithium titanate electrode material of example 1;
fig. 3 is an SEM image of an unmodified lithium titanate electrode material of example 1;
fig. 4 is a graph of cycle performance of modified lithium titanate electrode material and unmodified lithium titanate electrode material of example 1;
fig. 5 is a gas evolution diagram of a modified lithium titanate electrode material and an unmodified lithium titanate electrode material of example 1.
Detailed Description
The invention provides a preparation method of a modified lithium titanate electrode material, which comprises the following steps:
(1) mixing lithium dihydrogen phosphate, phenolic resin and a solvent to obtain a suspension;
(2) mixing the suspension and lithium titanate, evaporating to dryness and grinding to obtain powder;
(3) and carrying out heat treatment on the powder in an inert atmosphere to obtain the modified lithium titanate electrode material.
In the invention, the mass ratio of the lithium dihydrogen phosphate to the phenolic resin in the step (1) is preferably 1-10: 1 to 10, and more preferably 2 to 8: 2-8, more preferably 4-6: 4 to 6.
In the invention, the solid content of the suspension in the step (1) is preferably 0.1-1 g/L, more preferably 0.2-0.8 g/L, and even more preferably 0.4-0.6 g/L.
In the invention, two materials are used for coating at the same time, and the two coating materials can exert synergistic effect, so that the electronic and ionic conducting phases of lithium titanate are improved, and gas production behavior is inhibited.
In the present invention, the solvent in the step (1) is preferably an alcohol or an aqueous alcohol solution.
In the invention, the mass ratio of the lithium titanate to the lithium dihydrogen phosphate to the phenolic resin in the step (2) is preferably 94-99: 1-6, and more preferably 95-98: 2-5, more preferably 96-97: 3 to 4.
In the present invention, the particle size of the lithium titanate is preferably 100nm to 1 μm, more preferably 200 to 800nm, and still more preferably 400 to 600 nm.
In the invention, the mixing mode in the step (2) is preferably mechanical stirring, and the rotation speed of the mechanical stirring is preferably 400-500 rpm, more preferably 420-480 rpm, and more preferably 440-460 rpm; the mechanical stirring time is preferably 3-5 h, more preferably 3.4-4.6 h, and even more preferably 3.8-4.2 h.
In the invention, the temperature for evaporating in the step (2) is preferably 50-70 ℃, more preferably 54-66 ℃, and even more preferably 58-62 ℃.
In the present invention, the solvent is evaporated off by a step of evaporation to dryness.
In the invention, the rotation speed of the grinding in the step (2) is preferably 50-70 rpm, more preferably 54-66 rpm, and more preferably 58-62 rpm; the grinding time is preferably 2-3 h, more preferably 2.2-2.8 h, and even more preferably 2.4-2.6 h.
In the present invention, the inert atmosphere in the step (3) is preferably nitrogen or argon.
In the invention, the temperature of the heat treatment in the step (3) is preferably 700-800 ℃, more preferably 720-780 ℃, and even more preferably 740-760 ℃; the time of the heat treatment is preferably 1.5 to 2.5 hours, more preferably 1.6 to 2.4 hours, and even more preferably 1.8 to 2.2 hours.
In the invention, the lithium dihydrogen phosphate plays a catalytic role, so that the phenolic acid resin forms a graphitized carbon layer in the pyrolysis process; meanwhile, after heat treatment, the lithium dihydrogen phosphate is changed into lithium phosphate, the phenolic acid resin is changed into graphitized carbon, and the two coating materials act together to exert synergistic benefits, improve the quick charge and discharge performance of the lithium titanate and inhibit the gas production behavior of the lithium titanate.
The invention also provides a modified lithium titanate electrode material obtained by the preparation method.
In the modified lithium titanate electrode material, lithium phosphate and a carbon layer with a graphitized structure are interwoven together and coated on the surface of lithium titanate particles.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing phenolic resin, lithium dihydrogen phosphate and ethanol to obtain 0.5L of suspension with the solid content of 0.5g/L, wherein the mass ratio of the phenolic resin to the lithium dihydrogen phosphate is 1: 1; then adding 5g of lithium titanate into the suspension, wherein the particle size of the lithium titanate is 500nm, and stirring for 4 hours at 450 rpm; then evaporating to dryness at 60 ℃, completely evaporating ethanol, and grinding for 3 hours at 60rpm after evaporation to dryness to obtain powder;
and (3) placing the powder in a nitrogen atmosphere, and carrying out heat treatment at 750 ℃ for 2h to obtain the modified lithium titanate electrode material.
When the modified lithium titanate electrode material prepared in this example is observed, fig. 1 is an SEM image of the modified lithium titanate electrode material, fig. 2 is a TEM image of the modified lithium titanate electrode material, and it is apparent from fig. 1 and fig. 2 that an obvious coating exists on the surface of the modified lithium titanate electrode material.
When the unmodified lithium titanate electrode material is observed, fig. 3 is an SEM image of the unmodified lithium titanate battery material, and it can be seen from the SEM image that the surface of the unmodified lithium titanate battery material is smooth and no attachment exists.
The modified lithium titanate electrode material prepared in the embodiment and the lithium titanate electrode material which is not modified are subjected to performance tests:
assembling the button cell: 0.425g of the obtained modified lithium titanate composite negative electrode material is weighed, 0.05g of acetylene black serving as a conductive agent and 0.025gLA-132 serving as a binder are added, the mixture is uniformly ground and mixed in an agate mortar to prepare electrode slurry, the electrode slurry is uniformly coated on an aluminum foil, the electrode slurry is flaked and dried in a vacuum oven at the temperature of 70 ℃ for 12 hours to prepare an electrode slice, and the electrode slice is placed in a glove box. The electrode plate is taken as a working electrode, metal lithium is taken as a counter electrode, Celgard2400 is taken as a diaphragm, 1mol/L LiPF6/EC: DEC: DMC (volume ratio of 1:1:1) is taken as electrolyte, and a CR2032 button cell is assembled;
and (3) carrying out constant-current charge and discharge tests on the assembled CR2032 button cell at room temperature, wherein the test voltage range of the rate performance is 1.0V-3.0V, the charge and discharge rate is 0.2C, 5 times of cycle, and 10 times of 0.5C, 1.0C, 3.0C, 5.0C and 10.0C respectively, and then returning to 0.5C for 10 cycles. The first discharge specific capacity of the modified lithium titanate composite negative electrode material at 0.2 ℃ is 167mAh/g, the first discharge specific capacity at 3.0 ℃ is 142mAh/g, and the first discharge specific capacity at 10.0 ℃ is 128 mAh/g.
Assembling the button cell: weighing 0.425g of unmodified lithium titanate composite negative electrode material, adding 0.05g of acetylene black serving as a conductive agent and 0.025gLA-132 serving as a binder, uniformly grinding and mixing in an agate mortar to prepare electrode slurry, uniformly coating the electrode slurry on an aluminum foil, beating the electrode slurry, drying in a vacuum oven at the temperature of 70 ℃ for 12 hours to prepare an electrode slice, and putting the electrode slice into a glove box. The electrode plate is taken as a working electrode, metal lithium is taken as a counter electrode, Celgard2400 is taken as a diaphragm, 1mol/L LiPF6/EC: DEC: DMC (volume ratio of 1:1:1) is taken as electrolyte, and the CR2032 button cell is assembled.
And (3) carrying out constant-current charge and discharge tests on the assembled CR2032 button cell at room temperature, wherein the test voltage range of the rate performance is 1.0V-3.0V, the charge and discharge rate is 0.2C, 5 times of cycle, and 10 times of 0.5C, 1.0C, 3.0C, 5.0C and 10.0C respectively, and then returning to 0.5C for 10 cycles. The first discharge specific capacity of the modified LTO composite negative electrode material at 0.2C is 163mAh/g, the first discharge specific capacity at 3.0C is 124mAh/g, and the first discharge specific capacity at 10.0C is 72 mAh/g.
The experimental result is shown in fig. 4, and it can be seen that the rate capability of the modified lithium titanate electrode material is obviously superior to that of the unmodified lithium titanate electrode material.
Assembling the soft package battery: two 2645110 type soft package batteries are adopted, the thickness is 2.6mm, the width is 45mm, the length is 110mm, the positive electrode is lithium iron phosphate, the negative electrodes are respectively the modified lithium titanate electrode material and the unmodified lithium titanate electrode material of the embodiment, the capacity is designed to be 2600mAh, Celgard2400 is a diaphragm, 1mol/LLiPF6/EC: DEC: DMC (volume ratio is 1:1:1) is electrolyte, and the gas generation condition is observed after discharging at 1.0-2.7V and normal temperature and 0.2C/0.5C and circulating for 300 times.
The gas generation is shown in fig. 5, and it can be seen from the figure that the gas generation of the modified lithium titanate electrode material is significantly weaker than that of the unmodified lithium titanate electrode material.
Example 2
Mixing phenolic resin, lithium dihydrogen phosphate and ethanol to obtain 1L of suspension with the solid content of 0.8g/L, wherein the mass ratio of the phenolic resin to the lithium dihydrogen phosphate is 2: 1; then adding 20g of lithium titanate into the suspension, wherein the particle size of the lithium titanate is 400nm, and stirring for 5 hours at 500 rpm; then evaporating to dryness at 70 ℃, completely evaporating ethanol, and grinding for 3 hours at 50rpm after evaporation to dryness to obtain powder;
and (3) putting the powder in a nitrogen atmosphere, and carrying out heat treatment at 700 ℃ for 2.5h to obtain the modified lithium titanate electrode material.
Assembling the button cell: 0.425g of the obtained modified lithium titanate composite negative electrode material is weighed, 0.05g of acetylene black serving as a conductive agent and 0.025gLA-132 serving as a binder are added, the mixture is uniformly ground and mixed in an agate mortar to prepare electrode slurry, the electrode slurry is uniformly coated on an aluminum foil, the electrode slurry is flaked and dried in a vacuum oven at the temperature of 70 ℃ for 12 hours to prepare an electrode slice, and the electrode slice is placed in a glove box. The electrode plate is taken as a working electrode, metal lithium is taken as a counter electrode, Celgard2400 is taken as a diaphragm, 1mol/L LiPF6/EC: DEC: DMC (volume ratio of 1:1:1) is taken as electrolyte, and a CR2032 button cell is assembled;
and (3) carrying out constant-current charge and discharge tests on the assembled CR2032 button cell at room temperature, wherein the test voltage range of the rate performance is 1.0V-3.0V, the charge and discharge rate is 0.2C, 5 times of cycle, and 10 times of 0.5C, 1.0C, 3.0C, 5.0C and 10.0C respectively, and then returning to 0.5C for 10 cycles. The first discharge specific capacity of the modified lithium titanate composite negative electrode material at 0.2 ℃ is 163mAh/g, the first discharge specific capacity at 3.0 ℃ is 135mAh/g, and the first discharge specific capacity at 10.0 ℃ is 121 mAh/g.
Example 3
Mixing phenolic resin, lithium dihydrogen phosphate and ethanol to obtain 1L of suspension with the solid content of 1g/L, wherein the mass ratio of the phenolic resin to the lithium dihydrogen phosphate is 1: 2; then adding 18g of lithium titanate into the suspension, wherein the particle size of the lithium titanate is 800nm, and stirring for 5 hours at 400 rpm; then evaporating to dryness at 65 ℃, completely evaporating ethanol, and grinding for 2.5h at 70rpm after evaporation to dryness to obtain powder;
and (3) putting the powder in a nitrogen atmosphere, and carrying out heat treatment at 800 ℃ for 2.5h to obtain the modified lithium titanate electrode material.
Assembling the button cell: 0.425g of the obtained modified lithium titanate composite negative electrode material is weighed, 0.05g of acetylene black serving as a conductive agent and 0.025gLA-132 serving as a binder are added, the mixture is uniformly ground and mixed in an agate mortar to prepare electrode slurry, the electrode slurry is uniformly coated on an aluminum foil, the electrode slurry is flaked and dried in a vacuum oven at the temperature of 70 ℃ for 12 hours to prepare an electrode slice, and the electrode slice is placed in a glove box. The electrode plate is taken as a working electrode, metal lithium is taken as a counter electrode, Celgard2400 is taken as a diaphragm, 1mol/L LiPF6/EC: DEC: DMC (volume ratio of 1:1:1) is taken as electrolyte, and a CR2032 button cell is assembled;
and (3) carrying out constant-current charge and discharge tests on the assembled CR2032 button cell at room temperature, wherein the test voltage range of the rate performance is 1.0V-3.0V, the charge and discharge rate is 0.2C, 5 times of cycle, and 10 times of 0.5C, 1.0C, 3.0C, 5.0C and 10.0C respectively, and then returning to 0.5C for 10 cycles. The first discharge specific capacity of the modified lithium titanate composite negative electrode material at 0.2 ℃ is 162mAh/g, the first discharge specific capacity at 3.0 ℃ is 137mAh/g, and the first discharge specific capacity at 10.0 ℃ is 124 mAh/g.
From the above examples, it can be seen that the present invention provides a modified lithium titanate electrode material, in which the presence of phosphate can play a role in catalysis, so that a graphitized carbon layer is formed in the phenolic resin during pyrolysis. The graphitized carbon layer is beneficial to improving the electronic conductivity of lithium titanate, the lithium phosphate is beneficial to improving the lithium ion diffusion efficiency of lithium titanate, and in addition, the graphitized carbon layer and the lithium phosphate can both play a role in shielding the catalytic active sites on the surface of lithium titanate. The graphitized carbon layer and the lithium phosphate can exert synergistic benefits, namely the rapid charge and discharge performance of the lithium titanate is improved, and the gas production behavior of the lithium titanate is inhibited.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The preparation method of the modified lithium titanate electrode material is characterized in that the modified lithium titanate electrode material is a mixture of a lithium titanate surface-coated graphitized carbon layer and lithium phosphate, and the preparation method comprises the following steps:
(1) mixing lithium dihydrogen phosphate, phenolic resin and a solvent to obtain a suspension;
(2) mixing the suspension and lithium titanate, evaporating to dryness and grinding to obtain powder;
(3) carrying out heat treatment on the powder in an inert atmosphere to obtain the modified lithium titanate electrode material;
in the step (1), the mass ratio of lithium dihydrogen phosphate to phenolic resin is 1-10: 1-10;
the mass ratio of the lithium titanate to the lithium dihydrogen phosphate to the phenolic resin in the step (2) is 94-99: 1-6;
the particle size of the lithium titanate is 100 nm-1 mu m;
the rotation speed of the grinding in the step (2) is 50-70 rpm, and the grinding time is 2-3 h;
the temperature of the heat treatment in the step (3) is 720-800 ℃, and the time of the heat treatment is 1.5-2.5 h.
2. The method according to claim 1, wherein the suspension in the step (1) has a solid content of 0.1 to 1 g/L.
3. The method according to claim 1 or 2, wherein the solvent in the step (1) is an alcohol or an aqueous alcohol solution.
4. The method according to claim 3, wherein the mixing in step (2) is mechanical stirring, the rotation speed of the mechanical stirring is 400-500 rpm, and the time of the mechanical stirring is 3-5 h.
5. The method according to claim 4, wherein the temperature for evaporating in the step (2) is 50 to 70 ℃.
6. The modified lithium titanate electrode material obtained by the preparation method of any one of claims 1 to 5.
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| CN102244233A (en) * | 2011-05-18 | 2011-11-16 | 刘剑洪 | Method for preparing composite cathode material of graphene-like doped-cladded lithium titanate |
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