CN109888249B - Cobaltosic oxide and lithium titanate composite material, preparation method thereof and lithium ion battery - Google Patents
Cobaltosic oxide and lithium titanate composite material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
A cobaltosic oxide and lithium titanate composite material, a preparation method thereof and a lithium ion battery belong to the field of lithium ion batteries. The cobaltosic oxide and lithium titanate composite material comprises spinel lithium titanate and cobaltosic oxide, wherein the mass percentage of the cobaltosic oxide is 3-20%, and the balance is spinel lithium titanate. The preparation method comprises the following steps: reacting cobalt chloride with ammonia water to prepare cobalt hydroxide; and mixing the prepared cobalt hydroxide, titanium dioxide and lithium hydroxide, and carrying out hydrothermal reduction to obtain the cobaltosic oxide-lithium titanate composite material. The cobaltosic oxide and lithium titanate composite material is used as an active substance of a negative electrode material of a lithium ion battery, so that the conductivity is improved, particularly the first charge-discharge specific capacity is improved, meanwhile, the cycle stability of lithium titanate in the lithium ion battery is kept, the preparation method is simple, and the prepared lithium ion battery has high first discharge specific capacity and good cycle stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a cobaltosic oxide and lithium titanate composite material, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries are considered to be ideal power sources for portable electrical appliances and electric vehicles due to the advantages of high open circuit voltage, long cycle life, high energy density, low self-discharge rate and the like. At present, various lithium-intercalated carbon/graphite materials are mostly adopted as the cathode material of the commercial lithium ion battery. However, the carbonaceous negative electrode material forms a surface passivation film during the first cycle, which greatly consumes lithium ions in the positive electrode material, resulting in a large capacity loss. At the same time, the intrinsic safety of this material is not stable during high power impulse charging.
The theoretical specific capacity of the spinel type lithium titanate is 175 mAh/g. As an electrode material of a lithium ion battery with great prospect, spinel lithium titanate has the characteristic of zero strain that the skeleton structure hardly changes in the charging and discharging processes, has a good charging and discharging platform, is high in lithium intercalation potential, and is not easy to cause the precipitation of metal lithium; meanwhile, the electrolyte does not react with the electrolyte, and has very excellent cycle performance and safety performance. In addition, the lithium ions are diffused in the lithium titanate material quickly, and the high-rate charge-discharge performance of the lithium ion battery is improved. At present, lithium titanate ion battery pure electric buses have been widely used commercially due to the advantages of quick charging, long service life, high and low temperature resistance, high safety and the like.
However, Li is currently prepared4Ti5O12The negative electrode material still has the defects of poor conductivity, low density, small specific capacity and the like. The method for improving the specific capacity and the conductivity of the lithium titanate material by researching the lithium titanate material by using the methods of ion doping, surface coating and the like has strong industrial requirements, and has important scientific significance for improving the negative performance of the lithium titanate as the lithium ion battery material.
Disclosure of Invention
The invention aims to provide a cobaltosic oxide and lithium titanate composite material, a preparation method thereof and a lithium ion battery, wherein the cobaltosic oxide and lithium titanate composite material can be used as an active substance of a negative electrode material of the lithium ion battery, the preparation method adopts a hydrothermal reduction method to generate the cobaltosic oxide and lithium titanate composite material in situ, and the cobaltosic oxide and lithium titanate composite material is used as the active substance of the negative electrode material of the lithium ion battery, so that the conductivity is improved, particularly the first charge-discharge specific capacity is improved, meanwhile, the cycle stability of lithium titanate in the lithium ion battery is kept, the preparation method is simple, and the prepared lithium ion battery has high first discharge specific capacity and good cycle stability.
The invention relates to a cobaltosic oxide and lithium titanate composite material, which comprises spinel lithium titanate (Li)4Ti5O12) And cobaltosic oxide, wherein the mass percent of the cobaltosic oxide is 3-20%, and the balance is spinel lithium titanate.
The cobaltosic oxide is in a lamellar shape, the particle size of the cobaltosic oxide is 0.8-1.2 mu m, and the thickness of the cobaltosic oxide is 80-150 nm;
the spinel lithium titanate is granular, and the particle size of the spinel lithium titanate is 50-100 nm.
The cobaltosic oxide and lithium titanate composite material is a granular spinel lithium titanate material which is dispersedly distributed on the surface of lamellar cobaltosic oxide.
The preparation method of the cobaltosic oxide and lithium titanate composite material comprises the steps of reacting cobalt chloride with ammonia water to prepare cobalt hydroxide; and mixing the prepared cobalt hydroxide, titanium dioxide and lithium hydroxide, and carrying out hydrothermal reduction to obtain the cobaltosic oxide-lithium titanate composite material.
The preparation method of the cobaltosic oxide and lithium titanate composite material specifically comprises the following steps:
step 1: preparation of cobalt hydroxide
Reacting cobalt chloride with dilute ammonia water to obtain a reaction solution, dropwise adding pure ammonia water into the reaction solution to enable the pH value of the reaction solution to be 7.5-8.5 to obtain cobalt hydroxide precipitate, carrying out solid-liquid separation, and drying solid substances to obtain cobalt hydroxide;
wherein the molar concentration of the dilute ammonia water is 0.2-0.4 mol/L, and the molar ratio is as follows: OH in dilute ammonia water-＝1：(2～2.3)；
Step 2: hydrothermal reduction
According to the component proportion of the prepared cobaltosic oxide and lithium titanate composite material, mixing cobalt hydroxide, titanium dioxide and lithium hydroxide, adding the mixture into distilled water, placing the mixture into a high-temperature reaction kettle, heating the mixture to 160-190 ℃, preserving the heat for 8-12 hours, cooling the mixture to room temperature, carrying out solid-liquid separation, washing, leaching and drying the solid composite material to obtain the cobaltosic oxide and lithium titanate composite material; wherein, according to molar ratio, lithium hydroxide: titanium dioxide is 4: 5; the adding amount of the cobalt hydroxide is added according to the proportion of cobaltosic oxide in the prepared cobaltosic oxide and lithium titanate composite material.
In the step 1, the mass concentration of the pure ammonia water is 25-30%.
In the step 1, the solid-liquid separation is preferably suction filtration.
In the step 1, the drying is carried out at the drying temperature of 50-70 ℃ for 10-15 h.
The lithium ion battery cathode material adopts the cobaltosic oxide and lithium titanate composite material as an active substance.
The lithium ion battery negative electrode material also comprises a conductive agent and a binder.
A lithium ion battery negative electrode material is prepared by preferably mixing, by mass, a cobaltosic oxide and lithium titanate composite material: conductive agent: binder 8:1: 1.
A lithium ion battery adopts the lithium ion battery cathode material which takes the cobaltosic oxide and lithium titanate composite material as an active substance.
The lithium ion battery has the first charging specific capacity of 450-930mAh/g, the first discharging specific capacity of 680-1178 mAh/g, the 0.1A/g times discharging specific capacity of 140-170 mAh/g, the 0.1A/g multiplying power cycle of 80-90 times, and the capacity of more than 99%.
The cobaltosic oxide and lithium titanate composite material, the preparation method thereof and the lithium ion battery have the following principle and beneficial effects:
1. according to the cobaltosic oxide and lithium titanate composite material, lithium titanate is deposited on the flaky layer of cobaltosic oxide, the cobaltosic oxide can conduct ions, and most importantly, the cobaltosic oxide has the capability of storing Li ions, and when first charge and discharge are carried out, the cobaltosic oxide stores the Li ions firstly, so that the first charge and discharge specific capacity is remarkably improved;
the hydrothermal reduction method adopts the steps of firstly preparing alpha-type cobalt hydroxide, and in the hydrothermal reduction process, the alpha-type cobalt hydroxide is preferentially decomposed and dehydrated at high temperature to generate lamellar cobaltosic oxide, so that a place is provided for further generating lithium titanate, the lithium titanate is ensured not to be agglomerated, the circulation stability is good, and necessary conditions are provided for realizing the generation of the cobaltosic oxide and lithium titanate composite material in the last step;
the cobaltosic oxide generates an SEI film and has irreversible capacity, so that the first specific discharge capacity exceeds the theoretical value of 900mAh/g, but the cobaltosic oxide has higher specific discharge capacity, so that the cobaltosic oxide also has better specific discharge capacity with the material compounded by lithium titanate.
2. In the aspect of modification of the lithium titanate ion battery, the invention firstly carries out hydrothermal synthesis reaction on cobaltosic oxide and lithium titanate to prepare the cobaltosic oxide and lithium titanate composite material which is used as an active substance of a negative electrode material of the lithium ion battery.
3. The lithium titanate material in situ synthesized on the cobaltosic oxide material is prepared by using a hydrothermal reduction method, and the synthesis method is simpler and more practical than other methods, so that the preparation period of the composite material is greatly shortened.
4. When the cobalt hydroxide is prepared, dilute ammonia water is firstly used for reaction, and concentrated ammonia water is used for regulating the pH value, because the cobalt is amphoteric hydroxide and can react with alkali with different concentrations to generate materials with different valence states, the product required to be obtained in the invention is the cobalt hydroxide, so the cobalt hydroxide can only react with weak alkali, and after the reaction is completed, the concentrated ammonia water is used for regulating the pH value of the solution, so that the cobalt hydroxide can be precipitated from the solution.
Drawings
FIG. 1 is a scanning electron microscope image of a cobaltosic oxide and lithium titanate composite material prepared in example 1 of the present invention;
FIG. 2 is a spectral image analysis at the labeled spectrogram 2 of FIG. 1;
FIG. 3 is a graph of the first two charge-discharge curves for a cobaltosic oxide and lithium titanate composite material prepared in example 1 of the present invention;
FIG. 4 is a graph of rate performance of a cobaltosic oxide and lithium titanate composite material prepared in example 1 of the present invention cycling for 200 weeks;
fig. 5 is an ac impedance diagram of the cobaltosic oxide and lithium titanate composite material prepared in example 1 of the present invention.
Detailed Description
In order that the invention may be more readily understood, its advantages and features will be more readily understood by reference to the following detailed description of the invention taken in conjunction with the accompanying drawings.
These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
The chemical reagents used in the examples of the present invention are all analytical reagents and purchased from the national pharmaceutical group.
The experimental methods described in the present invention are all conventional methods unless otherwise specified.
The raw materials used in the present invention are commercially available unless otherwise specified.
Example 1
A cobaltosic oxide-lithium titanate composite material comprises spinel lithium titanate (Li)4Ti5O12) And cobaltosic oxide, wherein the mass percent of the cobaltosic oxide is 15%, and the balance is spinel lithium titanate.
A preparation method of a cobaltosic oxide and lithium titanate composite material specifically comprises the following steps:
1.1 preparation of cobalt hydroxide material:
weighing 1.5mg of cobalt chloride powder, dissolving the cobalt chloride powder in 30mL of 0.3mol/L dilute ammonia water solution, titrating with pure ammonia water until the pH value of the solution is 7.5-8.5, depositing for 12h, carrying out suction filtration treatment, and drying solid substances to obtain dried cobalt hydroxide powder.
1.2 hydrothermally reducing the prepared cobalt hydroxide, titanium dioxide and lithium hydroxide into a lithium titanate material which is self-generated in situ on a cobaltosic oxide material:
according to the proportion of cobaltosic oxide in the prepared cobaltosic oxide and lithium titanate composite material, mixing the dried cobaltosic oxide powder with lithium hydroxide and titanium dioxide in distilled water according to a certain proportion (wherein, the molar ratio of the lithium hydroxide to the titanium dioxide is 4:5, the experiment is that 15% of cobaltosic oxide is doped in the cobaltosic oxide and lithium titanate composite material), then placing the mixture in a reaction kettle, heating the mixture to 180 ℃ at high temperature, preserving the heat for 10 hours, cooling the mixture at room temperature, performing suction filtration after cooling, washing, suction filtration and drying the obtained solid composite material to obtain the lithium titanate material which is self-generated in situ on the cobaltosic oxide, namely the cobaltosic oxide and the composite material, wherein in the process, the cobaltosic oxide is decomposed into the cobaltosic oxide material after the cobalt hydroxide is heated at high temperature.
Examples of the experiments
Identification of Cobaltosic oxide and lithium titanate composite materials prepared by hydrothermal reduction method of example
1.1 scanning Electron microscopy analysis and energy Spectroscopy image analysis
(1) The cobaltosic oxide and lithium titanate composite material prepared in example 1 was scanned using a scanning electron microscope, and the scanning electron microscope image is shown in fig. 1.
As shown in fig. 1, the lamellar material is cobaltosic oxide material, and the granular material is lithium titanate material.
According to the graph 1, the lamellar cobaltosic oxide material with the particle size of 1.0 mu m and the thickness of 100nm is shown, the granular spinel lithium titanate material with the particle size of 50-100nm is dispersed and distributed on the surface of the lamellar cobaltosic oxide.
(2) And analyzing specific elements and contents according to the energy spectrum image.
Fig. 2 is a spectral image analysis of the labeled spectrogram 2 in fig. 1, and the elements and contents of the labeled spectrogram 2 in fig. 1 are shown in table 1 through analysis:
table 1 spectrum 2 element and content detection results
| General facial chart | ||||
| Element(s) | Line type | Weight percent of | Wt％Sigma | Atomic percent |
| O | K line system | 41.37 | 0.28 | 55.74 |
| C | K line system | 13.66 | 0.17 | 24.52 |
| Ti | K line system | 38.51 | 0.22 | 17.33 |
| Co | K line system | 5.40 | 0.13 | 1.98 |
| V | K line system | 0.33 | 0.08 | 0.14 |
| Si | K line system | 0.13 | 0.02 | 0.10 |
| Cu | L-shaped wire system | 0.40 | 0.14 | 0.14 |
| Zn | L-shaped wire system | 0.20 | 0.11 | 0.07 |
| Total amount of | 100.00 | 100.00 |
As can be seen from table 1 and fig. 2, there are obvious material elements such as Co and carbon C, Ti. The contents of V, Si and Cu are caused by the fact that the target material substrate is a copper material, and a slight punch-through phenomenon exists in the target material substrate.
1.2 first Charge/discharge Curve analysis
The cobaltosic oxide and lithium titanate composite material prepared in example 1 is used as an active substance to prepare a lithium ion battery cathode material, the lithium ion battery is prepared from the lithium ion battery cathode material, and then a charge-discharge experiment is carried out, wherein the previous two-time charge-discharge curve of the lithium ion battery prepared from the cobaltosic oxide and lithium titanate composite material is shown in fig. 3, and it can be clearly seen from fig. 3 that the first discharge specific capacity of the cobaltosic oxide and lithium titanate composite material is 1012mAh/g, the first charge specific capacity is 458mAh/g and is much higher than the theoretical specific capacity of lithium titanate of 175mAh/g, at this time, because the cobaltosic oxide generates an SEI film, the capacity is slightly higher than the theoretical specific capacity of the cobaltosic oxide of 900mAh/g, and the second discharge specific capacity is 448mAh/g, it can be seen that the doped cobaltosic oxide effectively improves the specific capacity of the cobaltosic oxide and lithium titanate composite material, the primary purpose of doping the cobaltosic oxide material is to improve the specific capacity of the cobaltosic oxide and lithium titanate composite material for the first charge and discharge, which also accords with the expected effect of the experiment. Compared with other materials such as carbon and the like, the performance of the material for charging and discharging the cobaltosic oxide doped material for the first time is more excellent.
1.3 Rate Performance Curve analysis
The rate performance analysis of the cobaltosic oxide and lithium titanate composite material is carried out, the rate performance curve of the cobaltosic oxide and lithium titanate composite material after 200 cycles is shown in fig. 4, and it can be seen from the rate performance curve (fig. 4) that the capacity of the material after 200 cycles is kept at 138mAh/g, the capacity retention rate is 99%, and the important point is that the specific capacity of the material under the condition of 0.1A/g and the specific capacity attenuation condition under the condition of 0.5A/g are very small, which shows that the cobaltosic oxide and lithium titanate composite material prepared by doping the cobaltosic oxide material in the experiment can improve the first charge and discharge performance of the cobaltosic oxide and lithium titanate composite material, and also improve the capacity retention rate of the cobaltosic oxide and lithium titanate composite material under different rates, so that the cobaltosic oxide and lithium titanate composite material have very good specific capacity under different rates. Meanwhile, the specific capacity of the cobaltosic oxide and lithium titanate composite material is improved, and the circulating stability of lithium titanate is well kept.
1.4 AC impedance Curve analysis
An alternating-current impedance diagram of the cobaltosic oxide and lithium titanate composite material is shown in a figure 5, according to curve analysis of the alternating-current impedance diagram, the internal resistance of the compounded cobaltosic oxide and lithium titanate composite material is 4.8, the internal resistance of pure lithium titanate is 6.2, the charge transfer impedance of the compounded cobaltosic oxide and lithium titanate composite material is 12, and the charge transfer impedance of the pure lithium titanate is 17, so that the fact that the conductivity of the material is obviously improved by the cobaltosic oxide and lithium titanate composite material can be clearly seen.
Example 2
A cobaltosic oxide-lithium titanate composite material comprises spinel lithium titanate (Li)4Ti5O12) And cobaltosic oxide, wherein the mass percent of the cobaltosic oxide is 9%, and the balance is spinel lithium titanate.
A preparation method of a cobaltosic oxide and lithium titanate composite material specifically comprises the following steps:
1.1 preparation of cobalt hydroxide material:
weighing 1.5mg of cobalt chloride powder, dissolving the cobalt chloride powder in 30mL of 0.3mol/L dilute ammonia water solution, titrating with pure ammonia water until the pH value of the solution is 7.5-8.5, depositing for 12h, carrying out suction filtration treatment, and drying solid substances to obtain dried cobalt hydroxide powder.
1.2 hydrothermally reducing the prepared cobalt hydroxide, titanium dioxide and lithium hydroxide into a lithium titanate material which is self-generated in situ on a cobaltosic oxide material:
according to the proportion of cobaltosic oxide in the prepared cobaltosic oxide and lithium titanate composite material, mixing the dried cobaltosic oxide powder with lithium hydroxide and titanium dioxide in distilled water according to a certain proportion (wherein the molar ratio of the lithium hydroxide to the titanium dioxide is 4:5, in the experiment, 9% of cobaltosic oxide is doped in the cobaltosic oxide and lithium titanate composite material), then placing the cobaltosic oxide and titanium dioxide composite material in a reaction kettle, heating the mixture to 180 ℃ at high temperature, preserving the temperature for 10h, cooling the mixture at room temperature, carrying out suction filtration treatment after cooling, washing, suction filtration and drying the obtained solid composite material to obtain the lithium titanate material which is self-generated in situ on the cobaltosic oxide, namely the cobaltosic oxide and lithium titanate composite material, wherein in the process, the cobaltosic oxide is decomposed into the cobaltosic oxide material after being heated at high temperature.
Example 3
A cobaltosic oxide-lithium titanate composite material comprises spinel lithium titanate (Li)4Ti5O12) And cobaltosic oxide, wherein the mass percent of the cobaltosic oxide is 6%, and the balance is spinel lithium titanate.
A preparation method of a cobaltosic oxide and lithium titanate composite material specifically comprises the following steps:
1.1 preparation of cobalt hydroxide material:
weighing 1.5mg of cobalt chloride powder, dissolving in 30mL of 0.3mol/L dilute ammonia water solution, titrating with pure ammonia water until the pH value of the solution is 7.5-8.5, depositing for 12h, performing suction filtration, and drying the solid substance at 60 ℃ for 12h to obtain the dried cobalt hydroxide powder.
1.2 hydrothermally reducing the prepared cobalt hydroxide, titanium dioxide and lithium hydroxide into a lithium titanate material which is self-generated in situ on a cobaltosic oxide material:
according to the proportion of cobaltosic oxide in the prepared cobaltosic oxide and lithium titanate composite material, mixing the dried cobaltosic oxide powder with lithium hydroxide and titanium dioxide in distilled water according to a certain proportion (wherein the molar ratio of the lithium hydroxide to the titanium dioxide is 4:5, in the experiment, 6% of cobaltosic oxide is doped in the cobaltosic oxide and lithium titanate composite material), then placing the mixture in a reaction kettle, heating the mixture to 190 ℃ at high temperature, keeping the temperature for 8h, cooling the mixture at room temperature, carrying out suction filtration treatment after cooling, washing, suction filtration and drying the obtained solid composite material to obtain the lithium titanate material which is in-situ self-generated on the cobaltosic oxide, namely the cobaltosic oxide and lithium titanate composite material, wherein in the process, the cobaltosic oxide is decomposed into the cobaltosic oxide material after being heated at high temperature.
Example 4
A cobaltosic oxide-lithium titanate composite material comprises spinel lithium titanate (Li)4Ti5O12) And cobaltosic oxide, wherein the mass percent of the cobaltosic oxide is 3%, and the balance is spinel lithium titanate.
A preparation method of a cobaltosic oxide and lithium titanate composite material specifically comprises the following steps:
1.1 preparation of cobalt hydroxide material:
weighing 1.5mg of cobalt chloride powder, dissolving in 30mL of 0.3mol/L dilute ammonia water solution, titrating with pure ammonia water until the pH value of the solution is 7.5-8.5, depositing for 12h, performing suction filtration, and drying the solid substance at 60 ℃ for 12h to obtain the dried cobalt hydroxide powder.
1.2 hydrothermally reducing the prepared cobalt hydroxide, titanium dioxide and lithium hydroxide into a lithium titanate material which is self-generated in situ on a cobaltosic oxide material:
according to the proportion of cobaltosic oxide in the prepared cobaltosic oxide and lithium titanate composite material, mixing the dried cobaltosic oxide powder with lithium hydroxide and titanium dioxide in distilled water according to a certain proportion (wherein the molar ratio of the lithium hydroxide to the titanium dioxide is 4:5, in the experiment, 13% of cobaltosic oxide is doped in the cobaltosic oxide and lithium titanate composite material), then placing the mixture in a reaction kettle, heating the mixture to 160 ℃ at high temperature, keeping the temperature for 12h, cooling the mixture at room temperature, carrying out suction filtration treatment after cooling, washing, suction filtration and drying the obtained solid composite material to obtain the lithium titanate material which is in-situ self-generated on the cobaltosic oxide, namely the cobaltosic oxide and lithium titanate composite material, wherein in the process, the cobaltosic oxide is decomposed into the cobaltosic oxide material after being heated at high temperature.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The cobaltosic oxide and lithium titanate composite material is characterized by comprising spinel lithium titanate and cobaltosic oxide, wherein the mass percent of the cobaltosic oxide is 3-20%, and the balance is the spinel lithium titanate;
the cobaltosic oxide and lithium titanate composite material is a granular spinel lithium titanate material which is dispersedly distributed on the surface of lamellar cobaltosic oxide;
the preparation method of the cobaltosic oxide and lithium titanate composite material specifically comprises the following steps:
step 1: preparation of cobalt hydroxide
Reacting cobalt chloride with dilute ammonia water to obtain a reaction solution, dropwise adding pure ammonia water into the reaction solution to enable the pH value of the reaction solution to be 7.5-8.5 to obtain cobalt hydroxide precipitate, carrying out solid-liquid separation, and drying solid substances to obtain cobalt hydroxide;
wherein the molar concentration of the dilute ammonia water is 0.2-0.4 mol/L, and the molar ratio is as follows: OH in dilute ammonia water-=1：(2~2.3)；
Step 2: hydrothermal reduction
According to the component proportion of the prepared cobaltosic oxide and lithium titanate composite material, mixing cobalt hydroxide, titanium dioxide and lithium hydroxide, adding the mixture into distilled water, placing the mixture into a high-temperature reaction kettle, heating the mixture to 160-190 ℃, preserving the heat for 8-12 hours, cooling the mixture to room temperature, carrying out solid-liquid separation, washing, leaching and drying the solid composite material to obtain the cobaltosic oxide and lithium titanate composite material; wherein, according to molar ratio, lithium hydroxide: titanium dioxide =4: 5; the adding amount of the cobalt hydroxide is added according to the proportion of cobaltosic oxide in the prepared cobaltosic oxide and lithium titanate composite material.
2. The cobaltosic oxide-lithium titanate composite material according to claim 1, wherein the cobaltosic oxide is in a lamellar form, has a particle size of 0.8 to 1.2 μm and a thickness of 80 to 150 nm;
the spinel lithium titanate is granular, and the particle size of the spinel lithium titanate is 50-100 nm.
3. A preparation method of a cobaltosic oxide and lithium titanate composite material, which is used for preparing the cobaltosic oxide and lithium titanate composite material as claimed in claim 1 or 2, and is characterized by comprising the following steps:
step 1: preparation of cobalt hydroxide
Reacting cobalt chloride with dilute ammonia water to obtain a reaction solution, dropwise adding pure ammonia water into the reaction solution to enable the pH value of the reaction solution to be 7.5-8.5 to obtain cobalt hydroxide precipitate, carrying out solid-liquid separation, and drying solid substances to obtain cobalt hydroxide;
wherein the molar concentration of the dilute ammonia water is 0.2-0.4 mol/L, and the molar ratio is as follows: OH in dilute ammonia water-=1：(2~2.3)；
Step 2: hydrothermal reduction
According to the component proportion of the prepared cobaltosic oxide and lithium titanate composite material, mixing cobalt hydroxide, titanium dioxide and lithium hydroxide, adding the mixture into distilled water, placing the mixture into a high-temperature reaction kettle, heating the mixture to 160-190 ℃, preserving the heat for 8-12 hours, cooling the mixture to room temperature, carrying out solid-liquid separation, washing, leaching and drying the solid composite material to obtain the cobaltosic oxide and lithium titanate composite material; wherein, according to molar ratio, lithium hydroxide: titanium dioxide =4: 5; the adding amount of the cobalt hydroxide is added according to the proportion of cobaltosic oxide in the prepared cobaltosic oxide and lithium titanate composite material.
4. The preparation method of the cobaltosic oxide and lithium titanate composite material according to claim 3, wherein in the step 1, the mass concentration of the pure ammonia water is 25-30%.
5. The method for preparing a cobaltosic oxide-lithium titanate composite material according to claim 3, wherein in the step 1, the solid-liquid separation is suction filtration; and drying at the temperature of 50-70 ℃ for 10-15 h.
6. A negative electrode material for a lithium ion battery, characterized in that the cobaltosic oxide-lithium titanate composite material according to claim 1 or 2 is used as an active material.
7. A lithium ion battery characterized by using the cobaltosic oxide-lithium titanate composite material according to claim 1 or 2 as an active material for preparing a negative electrode material of a lithium ion battery.
8. The lithium ion battery of claim 7, wherein the lithium ion battery has a first charging specific capacity of 450-930mAh/g, a first discharging specific capacity of 680-1178 mAh/g, a 0.1A/g multiple discharging specific capacity of 140-170 mAh/g, a 0.1A/g rate cycle of 80-90 times, and a capacity of more than 99%.
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| CN103730642A (en) * | 2014-01-24 | 2014-04-16 | 厦门大学 | Negative electrode material of lithium ion battery and preparation method thereof |
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