CN109346710B - Lithium titanate nitride-aluminum oxide nitride composite material and preparation method and application thereof - Google Patents
Lithium titanate nitride-aluminum oxide nitride composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lithium titanate nitride-aluminum oxide nitride composite material and a preparation method and application thereof, wherein the method comprises the following steps: respectively dissolving a lithium source and a titanium source in ethanol to obtain a lithium source solution and a titanium source solution; adding an aluminum source into a lithium source solution, mixing with a titanium source solution, adding acetic acid, stirring at 40-100 ℃ for 4-10 h, drying at 80-120 ℃, dispersing in deionized water, and spray drying to obtain a lithium titanate-aluminum oxide precursor; calcining for 4-18 h at 400-900 ℃ in air, cooling, and grinding to obtain lithium titanate-aluminum oxide composite powder; heating to 500-1000 ℃ in a protective atmosphere, and preserving heat for 0.5-2 h in a nitrogen-containing atmosphere to obtain the lithium titanate nitride-aluminum oxide nitride composite material. The composite material prepared by the invention has good high-rate performance, good safety performance and high specific capacity, and can be widely applied to lithium ion batteries and super capacitors required by various portable electronic devices and various electric vehicles.
Description
Technical Field
The invention relates to the field of electrode materials of lithium ion secondary batteries, in particular to a lithium titanate nitride-aluminum oxide nitride composite material and a preparation method and application thereof.
Background
The lithium titanate battery has the characteristics of safety, long service life, convenience and portability, so that the lithium titanate battery is widely applied to the field of numerous electronic products as a portable novel energy source. At present, the research direction of the negative electrode material for lithium ion battery is focused on the high ratioThe development of power battery materials with capacity, high multiplying power, high cycle performance and high safety performance is in the direction of development. The traditional carbon material has the characteristics of good low-rate performance and good cycle performance, and is the most used negative electrode material at the earliest time; however, the carbon material has a low theoretical capacity (372 mAh/g), and dendrites are easily formed at a low voltage to cause short circuit in the battery, so that the safety of large-current charging and discharging is poor, and people have to find a safe and reliable novel negative electrode material in which lithium is embedded at a slightly positive potential compared with a carbon negative electrode. Lithium titanate with a spinel structure is used as a negative electrode material, so that the charging and discharging voltage is improved, and two substances formed in the lithium deintercalation process have similar lattice parameters and small volume effect, and are called zero-strain materials. Li4Ti5O12At 1.5V (vs. Li/Li)+) The cathode material has a voltage platform on the left and right, charge and discharge efficiency close to 100 percent and excellent cycle performance, and is a power type lithium ion battery cathode material with great potential.
However, the lithium titanate material is used as a negative electrode material in the battery, and due to the characteristics of the lithium titanate material, the material and the electrolyte are easy to interact, and gas is generated in the cyclic charge and discharge process, so that the common lithium titanate battery is easy to expand, the battery core bulges, the electrical property is greatly reduced, and the theoretical cycle life of the lithium titanate battery is greatly reduced; and lithium titanate has poor electronic conductivity, which limits its high rate performance.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a lithium titanate nitride-aluminum oxide nitride composite material, and a preparation method and application thereof, and aims to solve the problems of poor safety performance, poor electronic conductivity and poor high rate performance of the conventional lithium titanate material.
The technical scheme of the invention is as follows:
a preparation method of a lithium titanate nitride-aluminum oxide nitride composite material comprises the following steps:
A. respectively dissolving a lithium source and a titanium source in ethanol to respectively obtain a lithium source solution and a titanium source solution; adding an aluminum source into a lithium source solution, mixing the aluminum source with a titanium source solution, adding acetic acid, heating and stirring at 40-100 ℃, drying at 80-120 ℃, dispersing in deionized water, and performing spray drying to obtain a lithium titanate-aluminum oxide precursor;
B. calcining a lithium titanate-aluminum oxide precursor in air at 400-900 ℃ for 4-18 h; cooling and grinding to prepare lithium titanate-aluminum oxide composite powder;
C. heating the lithium titanate-aluminum oxide composite powder to 500-1000 ℃ in a protective atmosphere, and then carrying out heat preservation on the lithium titanate-aluminum oxide composite powder for 0.5-2 hours at 500-1000 ℃ in a nitrogen-containing atmosphere to obtain the lithium titanate nitride-aluminum nitride composite material.
The preparation method of the lithium titanate nitride-aluminum oxide composite material comprises the step A, wherein in the step A, the lithium source is selected from one or more of lithium hydroxide, lithium acetate and lithium nitrate.
In the step A, the titanium source is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate and titanium tetrachloride.
In the preparation method of the lithium titanate nitride-aluminum oxide composite material, in the step A, the aluminum source is selected from one or more of aluminum nitrate, aluminum oxide and aluminum acetate.
The preparation method of the lithium titanate nitride-aluminum oxide composite material comprises the following steps of A, according to the molar ratio of Li to Ti to Al of 0.66-0.86: and adding the lithium source, the titanium source and the aluminum source at a ratio of 1: 0.01-0.2.
In the preparation method of the lithium titanate nitride-aluminum oxide composite material, in the step C, the protective atmosphere is argon, nitrogen, a mixed gas of argon and hydrogen, or a mixed gas of nitrogen and hydrogen.
In the step C, the nitrogen-containing atmosphere is nitrogen, ammonia, a mixed gas of nitrogen and hydrogen, a mixed gas of nitrogen and argon, a mixed gas of nitrogen and ammonia, or a mixed gas of ammonia and hydrogen.
A lithium titanate nitride-aluminum oxide nitride composite material is prepared by the preparation method of the lithium titanate nitride-aluminum oxide nitride composite material.
The application of the lithium titanate nitride-aluminum oxide composite material is described, wherein the lithium titanate nitride-aluminum oxide composite material is used as an electrode active substance of a fast-charging battery.
Has the advantages that: according to the invention, the interface conductivity of the material is improved by using aluminum nitride oxide, so that a lithium ion transmission channel is more smooth, the electronic conductivity of the surface of the material is improved by using lithium titanate nitride, and the transmission rate of electrons in the material is improved; therefore, the lithium titanate nitride-aluminum oxide nitride composite material has good high-rate performance, good safety performance and higher specific capacity, and can be widely applied to lithium ion batteries and super capacitors required by various portable electronic devices and various electric vehicles.
Drawings
Fig. 1 is a comparison graph of the first charge-discharge curves at 0.1C of lithium titanate nitride-aluminum oxide nitride composite materials prepared in examples 3, 5 and 6 of the present invention.
Fig. 2 is an XRD pattern of lithium titanate nitride-aluminum oxide nitride composite material prepared in example 4 of the present invention.
Fig. 3 is a first charge-discharge curve diagram of the lithium titanate nitride-aluminum oxide nitride composite material prepared in example 4 of the present invention at 0.1C.
Fig. 4 is a graph of cycle performance at 50C for a lithium titanate nitride-aluminum oxide nitride composite material prepared in example 4 of the present invention.
Fig. 5 is a coulombic efficiency curve at 50C for the lithium titanate nitride-aluminum oxide nitride composite material prepared in example 4 of the present invention.
Detailed Description
The invention provides a lithium titanate nitride-aluminum oxide nitride composite material, a preparation method and an application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of the lithium titanate nitride-aluminum oxide nitride composite material, which comprises the following steps:
A. respectively dissolving a lithium source and a titanium source in ethanol to respectively obtain a lithium source solution and a titanium source solution; adding an aluminum source into a lithium source solution, mixing the aluminum source with a titanium source solution, adding acetic acid, heating and stirring at 40-100 ℃ for 4-10 h, drying at 80-120 ℃, dispersing in deionized water, and performing spray drying to obtain a lithium titanate-aluminum oxide precursor;
B. calcining a lithium titanate-aluminum oxide precursor in air at 400-900 ℃ for 4-18 h; cooling and grinding to prepare lithium titanate-aluminum oxide composite powder;
C. heating the lithium titanate-aluminum oxide composite powder to 500-1000 ℃ in a protective atmosphere, and then carrying out heat preservation on the lithium titanate-aluminum oxide composite powder for 0.5-2 hours at 500-1000 ℃ in a nitrogen-containing atmosphere to obtain the lithium titanate nitride-aluminum nitride composite material.
The preparation method of the lithium titanate nitride-aluminum oxide nitride composite material provided by the embodiment has the characteristics of low preparation cost, simple and flexible preparation process and suitability for industrial large-scale production; the prepared composite material has good high rate performance and higher specific capacity, has excellent rate performance and cycle performance when being used as a negative active substance to be manufactured into a power battery, can be used for a lithium ion battery system required by an electric vehicle, and has the potential of replacing products such as a super capacitor and the like.
In a preferred embodiment, in step a, the lithium source may be selected from one or more of, but not limited to, lithium hydroxide, lithium acetate, lithium nitrate; the titanium source may be selected from one or more of, but is not limited to, tetrabutyl titanate, tetraisopropyl titanate, titanium tetrachloride; the aluminum source may be selected from one or more of, but not limited to, aluminum nitrate, aluminum oxide, aluminum acetate.
In a preferred embodiment, in the step A, the molar ratio of Li to Ti to Al is 0.66-0.86: and adding the lithium source, the titanium source and the aluminum source at a ratio of 1: 0.01-0.2.
In a preferred embodiment, in step C, the protective atmosphere is argon, nitrogen, a mixed gas of argon and hydrogen, or a mixed gas of nitrogen and hydrogen.
In a preferred embodiment, in step C, the nitrogen-containing atmosphere is nitrogen, ammonia, a mixed gas of nitrogen and hydrogen, a mixed gas of nitrogen and argon, a mixed gas of nitrogen and ammonia, or a mixed gas of ammonia and hydrogen.
The embodiment of the invention provides a lithium titanate nitride-aluminum oxide nitride composite material, which is prepared by adopting the preparation method of the lithium titanate nitride-aluminum oxide nitride composite material.
In the embodiment, the interface conductivity of the material is improved by using aluminum nitride oxide, so that a lithium ion transmission channel is more unobstructed, the electronic conductivity of the surface of the material is improved by using lithium titanate nitride, and the transmission rate of electrons in the material is improved; therefore, the lithium titanate nitride-aluminum oxide nitride composite material has good high-rate performance, good safety performance and higher specific capacity, and can be widely applied to lithium ion batteries and super capacitors required by various portable electronic devices and various electric vehicles. Specifically, the aluminum nitride oxide improves the grain boundary conductivity among material particles, and improves the lithium ion conductivity of the material; the lithium titanate nitride exists on the surface layer of the lithium titanate nitride-aluminum oxide nitride composite material in a Ti-N-O cross-linked structure, so that the surface of the lithium titanate nitride-aluminum oxide nitride composite material has high electron conductivity.
The embodiment of the invention provides an application of the lithium titanate nitride-aluminum oxide composite material, wherein the lithium titanate nitride-aluminum oxide composite material is used as an electrode active substance of a quick-charging battery.
In the embodiment, the lithium titanate nitride-aluminum oxide nitride composite material is used as an electrode active substance, and metal lithium is used as a negative electrode to prepare a half cell, so that the specific capacity can be as high as about 195mAh/g at the rate of 0.1C; the first charge-discharge specific capacity exceeds 123mAh/g when the 50C multiplying power is charged and discharged, and the discharge specific capacity is still higher than 118mAh/g after the 50C charging-discharging multiplying power is cycled for 10000 times.
Example 1
(1) Weighing anhydrous lithium acetate, tetrabutyl titanate and aluminum nitrate according to the molar ratio of Li to Ti to Al =0.84 to 1 to 0.05, taking ethanol as a dispersing agent, respectively dissolving the anhydrous lithium acetate and the tetrabutyl titanate in the ethanol, respectively preparing a lithium acetate solution and a tetrabutyl titanate solution, and dispersing the aluminum nitrate in the lithium acetate solution; then mixing tetrabutyl titanate solution with lithium acetate solution containing aluminum nitrate under the condition of stirring, adding acetic acid with the same volume, stirring for 6 hours at the temperature of 80 ℃, and drying at the temperature of 120 ℃; dispersing in deionized water to form a suspension, and carrying out spray drying on the suspension at the hot air temperature of 140 ℃ to obtain the lithium oxide-aluminum oxide precursor.
(2) Placing the lithium titanate-alumina precursor in a sintering furnace, heating to 600 ℃ at the speed of 5 ℃/min in the air, calcining for 8h at the temperature of 600 ℃, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the nano lithium titanate-alumina composite powder which is a nano material.
(3) Putting the lithium titanate-aluminum oxide composite powder into a three-section furnace, and heating to 600 ℃ in nitrogen; then the argon is changed into ammonia gas, the temperature is raised to 700 ℃ in the ammonia gas, and the temperature is kept for 0.5h, thus obtaining the lithium titanate nitride-aluminum oxide nitride composite material.
Electrochemical testing: taking the lithium titanate nitride-aluminum oxide nitride composite material prepared by the embodiment as an electrode active substance, acetylene black as a conductive agent, PVDF (polyvinylidene fluoride) as a binder, and NMP (N-methyl-2-pyrrolidone) as a solvent, mixing into slurry, and coating the slurry on a copper foil to prepare a pole piece; a lithium sheet is taken as a counter electrode, the concentration of electrolyte is 1mol/L, and a propylene microporous membrane is taken as a diaphragm of the battery to assemble a test battery; and assembling the button cell in a glove box filled with argon, and carrying out electrochemical test, wherein the charging and discharging voltage is 1-3V.
The battery is assembled by the method, and the first discharge specific capacity of the battery made of the active material with the heat preservation temperature of 700 ℃ is 191mAh/g and the charge specific capacity is 177mAh/g at 0.1 ℃.
Example 2
(1) The molar ratio of Li to Ti: weighing anhydrous lithium acetate, tetrabutyl titanate and aluminum oxide in a ratio of Al =0.86:1:0.1, respectively dissolving the anhydrous lithium acetate and the tetrabutyl titanate in ethanol by taking ethanol as a dispersing agent to respectively prepare a lithium acetate solution and a tetrabutyl titanate solution, and dispersing the aluminum oxide in the lithium acetate solution; mixing tetrabutyl titanate solution with lithium acetate solution containing aluminum oxide under stirring, adding acetic acid with the same volume, stirring at constant temperature of 80 ℃ for 8h, and drying at 120 ℃; then dispersing the precursor in deionized water to form a suspension, and carrying out spray drying on the suspension at the hot air temperature of 140 ℃ to obtain the lithium oxide-aluminum oxide precursor.
(2) Placing the lithium titanate-alumina precursor in a sintering furnace, heating to 500 ℃ at a speed of 5 ℃/min in the air, calcining for 6h at 500 ℃, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the lithium titanate-alumina composite powder which is a nano material.
(3) Putting the lithium titanate-aluminum oxide composite powder into a three-section furnace, and heating to 600 ℃ in argon; then, changing argon gas into ammonia gas, heating the ammonia gas to 700 ℃, and preserving the heat for 1h to obtain the lithium titanate nitride-aluminum oxide nitride composite material.
Electrochemical testing: the lithium titanate nitride-aluminum oxide nitride composite material prepared in the example is used as an electrode active substance, Super P (Super carbon) is used as a conductive agent, PVDF (polyvinylidene fluoride) is used as a binder, NMP (N-methyl-2-pyrrolidone) is used as a solvent, and the mixture is mixed into slurry and coated on a copper foil to prepare a pole piece. And (3) assembling a test battery by using a lithium sheet counter electrode, an electrolyte solution with the concentration of 1mol/L and a propylene microporous membrane as a battery diaphragm. And assembling the button cell in a glove box filled with argon, and performing electrochemical test, wherein the charging and discharging voltage is 1V-3V.
The battery is assembled by the method, and the first discharge specific capacity of the battery made of the active material with the heat preservation temperature of 700 ℃ is 185mAh/g at 0.1 ℃, and the charge specific capacity is 178 mAh/g.
Example 3
(1) The molar ratio of Li to Ti: al =0.78:1:0.15 weighing lithium acetate, tetrabutyl titanate and aluminum nitrate, taking ethanol as a dispersing agent, respectively dissolving the lithium acetate and the tetrabutyl titanate in the ethanol, respectively preparing a lithium acetate solution and a tetrabutyl titanate solution, dispersing the aluminum nitrate in the lithium acetate solution, mixing the tetrabutyl titanate solution and the lithium acetate solution containing the aluminum nitrate under the condition of stirring, adding acetic acid with the same volume, stirring for 4 hours at 80 ℃, and then drying at 120 ℃; dispersing the precursor in the deionized water to form a suspension, and carrying out spray drying on the suspension at the hot air temperature of 140 ℃ to prepare the lithium titanate-alumina precursor.
(2) Placing the lithium titanate-alumina precursor in a sintering furnace, heating to 800 ℃ at a speed of 5 ℃/min in the air, calcining for 4h at 800 ℃, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the lithium titanate-alumina composite powder which is a nano material.
(3) Putting the lithium titanate-aluminum oxide composite powder into a three-section furnace, and heating to 600 ℃ in argon; then the argon is changed into ammonia gas, the temperature is raised to 700 ℃ in the ammonia gas, and the temperature is kept for 0.5h, thus obtaining the lithium titanate nitride-aluminum oxide nitride composite material.
Electrochemical testing: the lithium titanate nitride-aluminum oxide nitride composite material prepared in the embodiment is used as an electrode active substance, Super P (Super carbon) is used as a conductive agent, PVDF (polyvinylidene fluoride) is used as a binder, NMP (N-methyl-2-pyrrolidone) is used as a solvent, and the mixture is mixed into slurry and coated on a copper foil to prepare a pole piece. And (3) assembling a test battery by using a lithium sheet counter electrode, an electrolyte solution with the concentration of 1mol/L and a propylene microporous membrane as a battery diaphragm. And assembling the button cell in a glove box filled with argon, and performing electrochemical test, wherein the charging and discharging voltage is 1V-3V.
The battery is assembled by the method, and the first charge-discharge curve of the battery made of the active material with the heat preservation at 700 ℃ at 0.1 ℃ is shown as a curve A in figure 1; the first discharge specific capacity is 168mAh/g, and the first charge specific capacity is 164 mAh/g.
Example 4
(1) The molar ratio of Li to Ti: weighing anhydrous lithium acetate, tetrabutyl titanate and aluminum oxide in a ratio of Al =0.86:1:0.1, respectively dissolving the anhydrous lithium acetate and the tetrabutyl titanate in ethanol by taking ethanol as a dispersing agent to respectively prepare a lithium acetate solution and a tetrabutyl titanate solution, and dispersing the aluminum oxide in the lithium acetate solution. Then mixing tetrabutyl titanate solution with lithium acetate solution containing aluminum oxide under the condition of stirring, adding acetic acid with the same volume, stirring for 4 hours at 80 ℃, and then drying at 120 ℃; dispersing in deionized water to form a suspension, and carrying out spray drying on the suspension at the hot air temperature of 140 ℃ to obtain the lithium oxide-aluminum oxide precursor.
(2) Placing the lithium titanate-alumina precursor in a sintering furnace, heating to 800 ℃ at a speed of 5 ℃/min in the air, calcining for 4h at 800 ℃, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the lithium titanate-alumina composite powder which is a nano material.
(3) Putting the lithium titanate-aluminum oxide composite powder into a three-section furnace, and heating to 600 ℃ in argon; and (3) replacing argon gas with ammonia gas, heating to 700 ℃ in the ammonia gas, and preserving the temperature for 0.5h to obtain the lithium titanate nitride and aluminum oxide nitride composite material, wherein the test result of X-ray diffraction (XRD) is shown in figure 2.
Electrochemical testing: the lithium titanate nitride-aluminum oxide nitride composite material prepared in the embodiment is used as an electrode active substance, Super P (Super carbon) is used as a conductive agent, PVDF (polyvinylidene fluoride) is used as a binder, NMP (N-methyl-2-pyrrolidone) is used as a solvent, and the mixture is mixed into slurry and coated on a copper foil to prepare a pole piece. And (3) assembling a test battery by using a lithium sheet counter electrode, an electrolyte solution with the concentration of 1mol/L and a propylene microporous membrane as a battery diaphragm. And assembling the button cell in a glove box filled with argon, and performing electrochemical test, wherein the charging and discharging voltage is 1V-3V.
The battery is assembled by the method, and the first charge-discharge curve of the battery made of the active material with the heat preservation temperature of 700 ℃ at 0.1 ℃ is shown in figure 3; the first discharge specific capacity is 198mAh/g, and the first charge specific capacity is 194 mAh/g. The lithium titanate nitride-aluminum oxide nitride composite material prepared in the embodiment is used as an electrode active substance, metal lithium is used as a negative electrode to prepare a half cell, and the cycle performance at 50 ℃ is shown in fig. 4, which shows that the first charge-discharge specific capacity exceeds 123mAh/g when 50C multiplying power is charged and discharged, and the discharge specific capacity is still higher than 116mAh/g after 50C charging and discharging multiplying power is cycled for 10000 times. The coulombic efficiency curve of the lithium titanate nitride-aluminum oxide nitride composite material prepared in the embodiment at 50C is shown in fig. 5, and it can be known that the lithium titanate nitride-aluminum oxide nitride composite material still maintains good coulombic efficiency after 50C charge-discharge multiplying power cycles 10000 times.
Example 5
(1) Weighing anhydrous lithium acetate, tetrabutyl titanate and aluminum nitrate according to the molar ratio of Li to Ti to Al =0.78 to 1 to 0.15, respectively dissolving the anhydrous lithium acetate and the tetrabutyl titanate in ethanol by taking ethanol as a dispersing agent to respectively prepare a lithium acetate solution and a tetrabutyl titanate solution, and then dispersing the aluminum nitrate in the lithium acetate solution; the tetrabutyl titanate solution and the lithium acetate solution containing aluminum nitrate were then mixed with stirring, and an equal volume of acetic acid was added. Stirring for 6h at 80 ℃, and drying at 120 ℃; dispersing the lithium titanate precursor in the deionized water to form a suspension, and carrying out spray drying on the suspension at the hot air temperature of 140 ℃ to obtain the lithium titanate precursor.
(2) Placing the lithium titanate-alumina precursor in a sintering furnace, heating to 800 ℃ at a speed of 5 ℃/min in the air, calcining for 4h at 800 ℃, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the lithium titanate-alumina composite powder which is a nano material.
(3) Putting the lithium titanate-aluminum oxide composite powder into a three-section furnace, and heating to 600 ℃ in nitrogen; then changing argon gas into ammonia gas, heating the ammonia gas to 600 ℃, and preserving the heat for 30 minutes to obtain the lithium titanate nitride-aluminum oxide nitride composite material.
Electrochemical testing: the lithium titanate nitride-aluminum oxide nitride composite material prepared in the embodiment is used as an electrode active substance, Super P (Super carbon) is used as a conductive agent, PVDF (polyvinylidene fluoride) is used as a binder, NMP (N-methyl-2-pyrrolidone) is used as a solvent, and the mixture is mixed into slurry and coated on a copper foil to prepare a pole piece. And (3) assembling a test battery by using a lithium sheet counter electrode, an electrolyte solution with the concentration of 1mol/L and a propylene microporous membrane as a battery diaphragm. Button cells were assembled in a glove box filled with argon and subjected to electrochemical testing. The charging and discharging voltage is 1V-3V.
The battery is assembled by the method, and the first charge-discharge curve of the battery made of the active material with the heat preservation at 600 ℃ at 0.1 ℃ is shown as a curve B in figure 1; the first discharge specific capacity is 165mAh/g, and the first charge specific capacity is 161 mAh/g.
Example 6
(1) Weighing anhydrous lithium acetate, tetrabutyl titanate and aluminum nitrate according to the molar ratio of Li to Ti to Al =0.78 to 1 to 0.15, respectively dissolving the anhydrous lithium acetate and the tetrabutyl titanate in ethanol by taking ethanol as a dispersing agent to respectively prepare a lithium acetate solution and a tetrabutyl titanate solution, and dispersing the aluminum nitrate in the lithium acetate solution; then mixing tetrabutyl titanate solution with lithium acetate solution containing aluminum nitrate under the condition of stirring, adding acetic acid with the same volume, stirring for 8 hours at the temperature of 80 ℃, and drying at the temperature of 120 ℃; then dispersing the precursor in deionized water to form a suspension, and carrying out spray drying on the suspension at the hot air temperature of 140 ℃ to obtain the lithium oxide-aluminum oxide precursor.
(2) Placing the lithium titanate-alumina precursor in a sintering furnace, heating to 800 ℃ at a speed of 5 ℃/min in the air, calcining for 4h at 800 ℃, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the lithium titanate-alumina composite powder which is a nano material.
(3) Putting the lithium titanate-aluminum oxide composite powder into a three-section furnace, and heating to 600 ℃ in nitrogen; then changing argon into nitrogen, heating to 800 ℃ in the nitrogen, and preserving the heat for 45 minutes to obtain the lithium titanate nitride-aluminum oxide nitride composite material.
Electrochemical testing: the lithium titanate nitride-aluminum oxide nitride composite material prepared in the embodiment is used as an electrode active substance, Super P (Super carbon) is used as a conductive agent, PVDF (polyvinylidene fluoride) is used as a binder, NMP (N-methyl-2-pyrrolidone) is used as a solvent, and the mixture is mixed into slurry and coated on a copper foil to prepare a pole piece. And (3) assembling a test battery by using a lithium sheet counter electrode, an electrolyte solution with the concentration of 1mol/L and a propylene microporous membrane as a battery diaphragm. And assembling the button cell in a glove box filled with argon, and performing electrochemical test, wherein the charging and discharging voltage is 1V-3V.
The battery is assembled by the method, and the first charge-discharge curve of the battery made of the active material with the heat preservation at 800 ℃ at 0.1 ℃ is shown as a curve C in figure 1; the first discharge specific capacity is 168mAh/g, and the first charge specific capacity is 162 mAh/g.
Example 7
(1) Weighing anhydrous lithium acetate, tetrabutyl titanate and aluminum nitrate according to the molar ratio of Li to Ti to Al =0.68 to 1 to 0.2, respectively dissolving the anhydrous lithium acetate and the tetrabutyl titanate in ethanol by taking ethanol as a dispersing agent to respectively prepare a lithium acetate solution and a tetrabutyl titanate solution, and dispersing the aluminum nitrate in the lithium acetate solution; then mixing tetrabutyl titanate solution with lithium acetate solution containing aluminum nitrate under the condition of stirring, adding acetic acid with the same volume, stirring for 6 hours at the temperature of 80 ℃, and drying at the temperature of 120 ℃; then dispersing the precursor in deionized water to form a suspension, and carrying out spray drying on the suspension at the hot air temperature of 140 ℃ to obtain the lithium oxide-aluminum oxide precursor.
(2) Placing the lithium titanate-alumina precursor in a sintering furnace, heating to 800 ℃ at the speed of 8 ℃/min in the air, calcining for 12h at the temperature of 800 ℃, naturally cooling to room temperature, grinding, and sieving with a 150-mesh sieve to obtain the nano lithium titanate-alumina composite powder which is a nano material.
(3) Putting the lithium titanate-aluminum oxide composite powder into a three-section furnace, and heating to 600 ℃ in nitrogen; and then changing argon into mixed gas of ammonia gas and nitrogen gas, heating the mixed gas to 700 ℃ in the mixed gas of ammonia gas and nitrogen gas, and preserving the heat for 1h to obtain the lithium titanate nitride-aluminum oxide nitride composite material.
Electrochemical testing: the lithium titanate nitride-aluminum oxide nitride composite material prepared in the embodiment is used as an electrode active substance, PVDF (polyvinylidene fluoride) is used as a binder, NMP (N-methyl-2-pyrrolidone) is used as a solvent, and the mixture is mixed into slurry to be coated on a copper foil to prepare a pole piece. And (3) assembling a test battery by using a lithium sheet counter electrode, an electrolyte solution with the concentration of 1mol/L and a propylene microporous membrane as a battery diaphragm. And assembling the button cell in a glove box filled with argon, and performing electrochemical test, wherein the charging and discharging voltage is 1V-3V.
The battery is assembled by the method, and the first discharge specific capacity of the battery made of the active material with the heat preservation temperature of 700 ℃ is 189mAh/g and the charge specific capacity is 177mAh/g at 0.1 ℃.
In summary, the invention provides a lithium titanate nitride-aluminum oxide nitride composite material, and a preparation method and application thereof. Specifically, the interface conductivity of the material is improved by using aluminum nitride oxide, so that a lithium ion transmission channel is smoother, the electron conductivity of the surface of the material is improved by using lithium titanate nitride, and the transmission rate of electrons in the material is improved; therefore, the lithium titanate nitride-aluminum oxide nitride composite material has good high-rate performance, good safety performance and higher specific capacity, and can be widely applied to lithium ion batteries and super capacitors required by various portable electronic devices and various electric vehicles.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (5)
1. A preparation method of a lithium titanate nitride-aluminum oxide nitride composite material is characterized by comprising the following steps:
A. respectively dissolving a lithium source and a titanium source in ethanol to respectively obtain a lithium source solution and a titanium source solution; adding an aluminum source into a lithium source solution, mixing the aluminum source with a titanium source solution, adding acetic acid, heating and stirring at 40-100 ℃ for 4-10 h, drying at 80-120 ℃, dispersing in deionized water, and performing spray drying to obtain a lithium titanate-aluminum oxide precursor;
B. calcining the lithium titanate-aluminum oxide precursor in air at 400-900 ℃ for 4-18 h, cooling, and grinding to prepare lithium titanate-aluminum oxide composite powder;
C. heating the lithium titanate-aluminum oxide composite powder to 500-1000 ℃ in a protective atmosphere, and then carrying out heat preservation on the lithium titanate-aluminum oxide composite powder for 0.5-2 hours at 500-1000 ℃ in a nitrogen-containing atmosphere to obtain a lithium titanate nitride-aluminum nitride composite material;
in the step A, the lithium source is selected from one or more of lithium hydroxide, lithium acetate and lithium nitrate; the aluminum source is selected from one or more of aluminum nitrate, aluminum oxide and aluminum acetate; the titanium source is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate and titanium tetrachloride; and adding the lithium source, the titanium source and the aluminum source according to the molar ratio of Li to Ti to Al of (0.66-0.86) to 1 of (0.01-0.2).
2. The method of preparing a lithium titanate nitride-aluminum oxide composite material according to claim 1, wherein in step C, the protective atmosphere is argon, nitrogen, a mixture of argon and hydrogen, or a mixture of nitrogen and hydrogen.
3. The method for preparing a lithium titanate nitride-aluminum oxide composite material according to claim 1, wherein in the step C, the nitrogen-containing atmosphere is nitrogen, ammonia, a mixed gas of nitrogen and hydrogen, a mixed gas of nitrogen and argon, a mixed gas of nitrogen and ammonia, or a mixed gas of ammonia and hydrogen.
4. A lithium titanate nitride-aluminum oxide composite material is characterized by being prepared by the preparation method of the lithium titanate nitride-aluminum oxide composite material according to any one of claims 1-3.
5. Use of the lithium titanate nitride-aluminum oxide composite material according to claim 4 as an electrode active material for a fast-charging battery.
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| CN115231612B (en) * | 2022-09-20 | 2023-02-03 | 河北格力钛新能源有限公司 | Method for preparing modified lithium titanate composite material and modified lithium titanate composite material |
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