CN111564621A - Lithium battery anode composite material and preparation method and application thereof - Google Patents
Lithium battery anode composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a lithium battery anode composite material, which is formed by compounding a nano magnesium-lithium alloy, lanthanum copper aluminate and graphite, wherein the average crystal grain of the nano magnesium-lithium alloy is between 5 and 15nm, the graphite and the nano magnesium-lithium alloy are used as matrixes, and the lanthanum copper aluminate is coated on the surface of the matrix to form the composite material. The preparation method of the lithium battery anode composite material is simple, and the prepared material has the advantages of good in-store type, mechanical and electrical properties, good high and low temperature resistance, and can be applied to the quick-charging lithium ion battery, and the cycle performance of the lithium ion battery can be obviously improved.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a lithium battery anode composite material and a preparation method and application thereof.
Background
Lithium ion batteries have witnessed the modern, briskly developed electronic technology and become an essential part of modern ubiquitous portable electronic devices. Lithium electrochemical cells, more commonly referred to as batteries (packs), are widely used in a variety of military and commercial products. Many of these products use high energy and high power batteries. Due in part to the miniaturization of portable electronic devices, it is desirable to develop smaller lithium batteries with increased power capacity and service life. However, with the demand for more and more advanced devices having high energy and power, especially the development of hybrid electric vehicles, it has been difficult for the performance of commercial lithium ion batteries to achieve their desired performance. One important reason is that the current anode main material of the lithium ion battery is graphite, the theoretical capacity of the lithium ion battery is only 372mAh/g, the lithium storage capacity of the lithium ion battery is not high enough, and the requirement that the future lithium ion battery must be developed towards high capacity cannot be met; also during battery operation, lithium dendrites are likely to form on the graphite surface, easily inducing safety problems. Therefore, extensive research has been devoted to finding effective methods to achieve better anode materials.
Transition metal oxides are those which have a high capacity and a relatively high operating voltage compared to graphite, and in addition, can avoid the problem of lithium dendrite formation using graphite. However, during the lithium intercalation and deintercalation cycle, the transition metal oxide anode material has severe volume expansion and contraction, causing the structural damage and mechanical pulverization of the material, thereby causing the degradation of the cycling performance of the electrode. It is an important research subject in lithium batteries to solve this problem and to improve the capacity of lithium batteries.
Disclosure of Invention
The invention aims to provide a lithium battery anode composite material and a preparation method and application thereof, the preparation method is simple, the prepared material has the advantages of good in-store type, mechanical and electrical properties, can obviously improve the cycle performance of a lithium ion battery, has good high and low temperature resistance, and can be applied to a quick-charging lithium ion battery.
The technical scheme of the invention is realized as follows:
the invention provides a lithium battery anode composite material, which is formed by compounding a nano magnesium-lithium alloy, lanthanum copper aluminate and graphite, wherein the average crystal grain of the nano magnesium-lithium alloy is between 5 and 15nm, the graphite and the nano magnesium-lithium alloy are used as matrixes, and the lanthanum copper aluminate is coated on the surface of the matrix to form the composite material.
As a further improvement of the invention, the mass ratio of the nano magnesium-lithium alloy, the lanthanum copper aluminate and the graphite is (3-10): (2-7): 50.
as a further improvement of the invention, the mass ratio of the nano magnesium-lithium alloy, the lanthanum copper aluminate and the graphite is 7: 5: 50.
as a further improvement of the invention, the preparation method of the nano magnesium-lithium alloy comprises the following steps: and grinding the magnesium-lithium alloy by a planetary ball mill, washing by deionized water, and drying to obtain the nano magnesium-lithium alloy.
Further, the grinding rotation speed is 550-.
The preparation method of the lanthanum copper aluminate comprises the following steps: adding copper nitrate, lanthanum nitrate and aluminum nitrate into ethylene glycol, stirring and mixing uniformly, dropwise adding NaOH solution to adjust the pH value, continuously stirring for 30-60min, transferring into a polytetrafluoroethylene inner container, placing into a stainless steel hot reaction kettle, sealing, placing into a drying oven for reacting for 12-24h at the temperature of 150 ℃ and 170 ℃, cooling, removing the supernatant, washing a solid product with deionized water, and drying to obtain the lanthanum copper aluminate.
As a further improvement of the invention, the mass ratio of the copper nitrate, lanthanum nitrate and aluminum nitrate is 3: 1: (3-5).
As a further improvement of the invention, the NaOH solution has a mass concentration of 3-5 mol/L; the pH value is adjusted to 9-10; the volume ratio of the total mass of the copper nitrate, the lanthanum nitrate and the aluminum nitrate to the glycol is (7-9): 50.
the invention further provides a preparation method of the lithium battery anode composite material, which comprises the following steps: and grinding graphite to below 200 meshes, fully mixing the graphite with the nano magnesium-lithium alloy and the lanthanum copper aluminate, grinding by using a planetary ball mill, drying and tabletting to obtain the lithium battery anode composite material.
As a further improvement of the invention, the rotation speed of the planetary ball mill is 450-550r/min, and the time is 1-3 h.
The invention further protects the application of the lithium battery anode composite material in preparing the fast-charging lithium battery anode.
The invention has the following beneficial effects: the lanthanum copper aluminate prepared by the method has large surface tension, organic solvent molecules are difficult to embed into electrode lattices, and the damage of the embedding of the solvent molecules to an electrode structure can be well prevented; the surface has a plurality of gaps, so that the contact area between the electrode and the electrolyte can be greatly increased, and the wettability of the electrode material and an organic solvent is conveniently improved; the surface defects are likely to generate sub band gaps, so that the discharge curve of the electrode is smoother, and the cycle life of the electrode is prolonged; the lanthanum copper aluminate powder with the micro-nano structure has large specific surface area, an anisotropic interface accounts for 1% -5% of the material, and the electrode has a plurality of interface reaction positions during lithium intercalation and deintercalation, so that the polarization phenomenon in the electrochemical process of the electrode can be reduced; the reaction mechanism of lanthanum copper aluminate is as follows:
Al3++4OH-=AlO2 -+2H2O
Cu2++La3++AlO2 -=CuLa(AlO2)5
the formed lanthanum copper aluminate has better lattice property and has the following advantages: (1) the surface tension is large, organic solvent molecules are difficult to embed into electrode lattices, and the damage of the embedding of the solvent molecules to an electrode structure can be well prevented; (2) the surface has a plurality of gaps, so that the contact area between the electrode and the electrolyte can be greatly increased, and the wettability of the electrode material and an organic solvent is conveniently improved; (3) the surface defects are likely to generate sub band gaps, so that the discharge curve of the electrode is smoother, and the cycle life of the electrode is prolonged; (4) the specific surface area of the powder is large, the anisotropic interface accounts for 1-5% of the material, and the electrode has a plurality of interface reaction positions during lithium intercalation and deintercalation, thereby being beneficial to reducing the polarization phenomenon in the electrochemical process of the electrode.
The added nano magnesium-lithium alloy has higher theoretical capacity and a lithium embedding platform. Meanwhile, the conductive adhesive has the advantages of good processability, good conductivity, low solvent co-intercalation and the like. On the other hand, the battery has extremely low density and light weight, can effectively reduce the mechanical stress of the material and stabilize the material structure, so that the cycle performance and reversible capacity of the battery are higher;
the nano magnesium-lithium alloy material can obtain a high-performance anode material which is easy to use without a lithium cathode material, is easy for industrial production, can prepare a nano-crystalline metal alloy under a mild condition, has high surface tension, is difficult to embed organic solvent molecules into an electrode lattice, and can well prevent the embedding of the solvent molecules from damaging an electrode structure; the surface of the anode material is provided with a plurality of gaps, so that the contact area between the electrode and electrolyte can be greatly increased, the wettability of the electrode material and an organic solvent is conveniently improved, sub-band gaps are possibly generated due to surface defects, the discharge curve of the electrode is smoother, the cycle life of the electrode is prolonged, the electrical property of the anode material can be improved, the anode material is prepared by mixing the nano magnesium-lithium alloy and the lanthanum copper aluminate, the graphite is used as a matrix, the electrical property can be obviously improved, and the synergistic effect is achieved.
The preparation method of the lithium battery anode composite material is simple, and the prepared material has the advantages of good in-store type, mechanical and electrical properties, good high and low temperature resistance, and can be applied to the quick-charging lithium ion battery, and the cycle performance of the lithium ion battery can be obviously improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The magnesium-lithium alloy is L91 magnesium-lithium alloy, and is available from Jiazhou metal materials Co., Ltd.
Copper nitrate, CAS No.: 10031-43-3.
Lanthanum nitrate, CAS No.: 100587-94-8.
Aluminum nitrate, CAS No.: 13473-90-0. All chemicals were purchased from the national pharmaceutical group.
The planetary ball mill is a phi 1830-4500 planetary ball mill, which is available from Changyi mining machinery Co., Ltd.
Example 1 preparation method of lithium battery anode composite material
The method comprises the following steps:
s1, the preparation method of the nano magnesium-lithium alloy comprises the following steps: grinding the magnesium-lithium alloy by a planetary ball mill at the grinding speed of 550r/min for 10h, washing with deionized water, and drying to obtain a nano magnesium-lithium alloy;
s2, adding 3g of copper nitrate, 1g of lanthanum nitrate and 3g of aluminum nitrate into 50mL of ethylene glycol, uniformly stirring and mixing, dropwise adding 3mol/L of NaOH solution to adjust the pH value to 9, continuously stirring for 30min, transferring into a polytetrafluoroethylene inner container, placing into a stainless steel hydrothermal reaction kettle, sealing, placing into an oven to react for 12h at 150 ℃, cooling, removing a supernatant, washing a solid product with deionized water, and drying to obtain lanthanum copper aluminate;
s3, grinding 50g of graphite to below 200 meshes, fully mixing the graphite with 3g of nano magnesium-lithium alloy and 2g of lanthanum copper aluminate, grinding the mixture by using a planetary ball mill at the rotating speed of 450r/min for 1h, drying and tabletting to obtain the lithium battery anode composite material.
EXAMPLE 2 preparation of lithium Battery Anode composite Material
The method comprises the following steps:
s1, the preparation method of the nano magnesium-lithium alloy comprises the following steps: grinding the magnesium-lithium alloy by a planetary ball mill at the grinding speed of 1000r/min for 15h, washing with deionized water, and drying to obtain a nano magnesium-lithium alloy;
s2, adding 3g of copper nitrate, 1g of lanthanum nitrate and 5g of aluminum nitrate into 50mL of ethylene glycol, uniformly stirring and mixing, dropwise adding 5mol/L of NaOH solution to adjust the pH value to 10, continuously stirring for 60min, transferring into a polytetrafluoroethylene inner container, placing into a stainless steel hydrothermal reaction kettle, sealing, placing into an oven to react for 24h at 170 ℃, cooling, removing a supernatant, washing a solid product with deionized water, and drying to obtain lanthanum copper aluminate;
s3, grinding 50g of graphite to below 200 meshes, fully mixing with 10g of nano magnesium-lithium alloy and 7g of lanthanum copper aluminate, grinding by using a planetary ball mill at the rotating speed of 550r/min for 3h, drying, and tabletting to obtain the lithium battery anode composite material.
EXAMPLE 3 preparation of lithium Battery Anode composite Material
The method comprises the following steps:
s1, the preparation method of the nano magnesium-lithium alloy comprises the following steps: grinding the magnesium-lithium alloy by a planetary ball mill at the grinding speed of 700r/min for 12h, washing with deionized water, and drying to obtain a nano magnesium-lithium alloy;
s2, adding 6g of copper nitrate, 2g of lanthanum nitrate and 8g of aluminum nitrate into 100mL of ethylene glycol, uniformly stirring and mixing, dropwise adding a 4mol/L NaOH solution to adjust the pH value to 8.5, continuously stirring for 45min, transferring into a polytetrafluoroethylene inner container, placing into a stainless steel hot reaction kettle, sealing, placing into an oven to react for 18h at 160 ℃, cooling, removing a supernatant, washing a solid product with deionized water, and drying to obtain lanthanum copper aluminate;
s3, grinding 50g of graphite to below 200 meshes, fully mixing with 7g of nano magnesium-lithium alloy and 5g of lanthanum copper aluminate, grinding by using a planetary ball mill at the rotating speed of 500r/min for 2h, drying, and tabletting to obtain the lithium battery anode composite material.
Comparative example 1
Compared with the embodiment 3, the nano magnesium-lithium alloy is not added, and other conditions are not changed.
The method comprises the following steps:
s1, adding 6g of copper nitrate, 2g of lanthanum nitrate and 8g of aluminum nitrate into 100mL of ethylene glycol, uniformly stirring and mixing, dropwise adding a 4mol/L NaOH solution to adjust the pH value to 8.5, continuously stirring for 45min, transferring into a polytetrafluoroethylene inner container, placing into a stainless steel hot reaction kettle, sealing, placing into an oven to react for 18h at 160 ℃, cooling, removing a supernatant, washing a solid product with deionized water, and drying to obtain lanthanum copper aluminate;
s2, grinding 50g of graphite to below 200 meshes, fully mixing the graphite with 12g of lanthanum copper aluminate, grinding by using a planetary ball mill at the rotating speed of 500r/min for 2 hours, drying, and tabletting to obtain the lithium battery anode composite material.
Comparative example 2
Compared with the example 3, no lanthanum copper aluminate is added, and other conditions are not changed.
The method comprises the following steps:
s1, the preparation method of the nano magnesium-lithium alloy comprises the following steps: grinding the magnesium-lithium alloy by a planetary ball mill at the grinding speed of 700r/min for 12h, washing with deionized water, and drying to obtain a nano magnesium-lithium alloy;
s2, grinding 50g of graphite to below 200 meshes, fully mixing the graphite with 12g of nano magnesium-lithium alloy, grinding the mixture by using a planetary ball mill at the rotating speed of 500r/min for 2 hours, drying and tabletting to obtain the lithium battery anode composite material.
Test example 1
Composite materials prepared in examples 1-3 and comparative examples 1-2 of the present invention were pressed into lithium battery anode materials, and commercially available lithium battery anode materials (purchased from shanghai jejie new material science and technology), and button cells were prepared using metal lithium as a counter electrode, and subjected to charge-discharge and cycle tests, and a charge-discharge curve was obtained at a current density of 300 mA/g. According to the invention, the porous copper is used as the matrix, so that the matrix is directly used as the current collector in the subsequent preparation process of the lithium battery, and the step of manufacturing the current collector is omitted.
The results are shown in Table 1.
TABLE 1
The test result shows that the energy density of the battery is 800-. The number of battery cycles experienced when the battery capacity had decayed to 80% of the rated capacity reached 2315, which was significantly better than comparative examples 1-2 and the commercially available anode materials.
Compared with the example 3, the comparative examples 1 and 2 have no addition of the nano magnesium lithium alloy or the nano lanthanum copper aluminate, and the number of battery cycle times is obviously reduced when the battery energy density and the battery capacity are attenuated to 80% of the rated capacity, so that the nano magnesium lithium alloy or the nano lanthanum copper aluminate has a synergistic effect on the performance of the lithium battery. The nano magnesium-lithium alloy material can obtain a high-performance anode material which is easy to use without a lithium cathode material, is easy for industrial production, can prepare a nano-crystalline metal alloy under a mild condition, has high surface tension, is difficult to embed organic solvent molecules into an electrode lattice, and can well prevent the embedding of the solvent molecules from damaging an electrode structure; the surface of the anode material is provided with a plurality of gaps, so that the contact area between the electrode and electrolyte can be greatly increased, the wettability of the electrode material and an organic solvent is conveniently improved, sub-band gaps are possibly generated due to surface defects, the discharge curve of the electrode is smoother, the cycle life of the electrode is prolonged, the electrical property of the anode material can be improved, the anode material is prepared by mixing the nano magnesium-lithium alloy and the lanthanum copper aluminate, the graphite is used as a matrix, the electrical property can be obviously improved, and the synergistic effect is achieved.
Test example 2
The composite materials prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2 were pressed into lithium battery anode materials, and commercially available lithium battery anode materials (available from shanghai jejie new materials science and technology) were prepared into lithium batteries, charged at room temperature (25 ℃) and a constant current of about 0.5C rate until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, and then discharged at a constant current of 0.5C rate until the voltage reached 2.75V.
During the second cycle, the lithium battery was charged at a constant current of about 0.5C rate until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, and then discharged at a constant current of 0.2C rate until the voltage reached 2.80V.
During the third cycle, the lithium battery was charged at a constant current of about 0.5C rate until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, and then discharged at a constant current of 0.2C rate until the voltage reached 2.80V. The discharge capacity in the third cycle was regarded as a standard capacity.
During the fourth cycle, the lithium cell was charged at a rate of about 0.5C until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, stored in an oven at 60 ℃ for 60 days, and then the cell was removed and subjected to a fourth discharge cycle at a rate of 0.1C until the voltage reached 2.75V. Some charge and discharge results are shown in table 4 below. The capacity retention rate after high-temperature storage can be defined as follows.
Capacity retention after high-temperature storage [% ] is [ discharge capacity/standard capacity after high-temperature exposure in the fourth cycle ] × 100%.
(Standard Capacity is discharge Capacity in third cycle)
TABLE 2
Group of | Capacity retention (%) |
Example 1 | 89.45 |
Example 2 | 91.23 |
Example 3 | 88.32 |
Comparative example 1 | 80.12 |
Comparative example 2 | 79.23 |
Comparative example 3 | 75.34 |
Is commercially available | 82.55 |
As shown in table 4 above, lithium batteries prepared including the anode materials of examples 1 to 3 of the present invention showed significantly increased stability at high temperatures, compared to lithium batteries manufactured in comparative examples 1 to 2 and commercially available anode materials.
Compared with the prior art, the lanthanum copper aluminate prepared by the method has large surface tension, organic solvent molecules are difficult to embed into electrode lattices, and the damage of the embedding of the solvent molecules to an electrode structure can be well prevented; the surface has a plurality of gaps, so that the contact area between the electrode and the electrolyte can be greatly increased, and the wettability of the electrode material and an organic solvent is conveniently improved; the surface defects are likely to generate sub band gaps, so that the discharge curve of the electrode is smoother, and the cycle life of the electrode is prolonged; the lanthanum copper aluminate powder with the micro-nano structure has large specific surface area, an anisotropic interface accounts for 1% -5% of the material, and the electrode has a plurality of interface reaction positions during lithium intercalation and deintercalation, so that the polarization phenomenon in the electrochemical process of the electrode can be reduced;
the added nano magnesium-lithium alloy has higher theoretical capacity and a lithium embedding platform. Meanwhile, the conductive adhesive has the advantages of good processability, good conductivity, low solvent co-intercalation and the like. On the other hand, the battery has extremely low density and light weight, can effectively reduce the mechanical stress of the material and stabilize the material structure, so that the cycle performance and reversible capacity of the battery are higher;
the preparation method of the lithium battery anode composite material is simple, and the prepared material has the advantages of good in-store type, mechanical and electrical properties, good high and low temperature resistance, and can be applied to the quick-charging lithium ion battery, and the cycle performance of the lithium ion battery can be obviously improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The composite material is characterized by being formed by compounding a nano magnesium-lithium alloy, lanthanum copper aluminate and graphite, wherein the average crystal grain of the nano magnesium-lithium alloy is 5-15nm, the graphite and the nano magnesium-lithium alloy are used as a matrix, and the lanthanum copper aluminate is coated on the surface of the matrix to form the composite material.
2. The lithium battery anode composite material as claimed in claim 1, wherein the mass ratio of the nano magnesium-lithium alloy, the lanthanum copper aluminate and the graphite is (3-10): (2-7): 50.
3. the lithium battery anode composite material as claimed in claim 2, wherein the mass ratio of the nano magnesium-lithium alloy, the lanthanum copper aluminate and the graphite is 7: 5: 50.
4. the lithium battery anode composite material as claimed in claim 1, wherein the nano magnesium-lithium alloy is prepared by the following steps: and grinding the magnesium-lithium alloy by a planetary ball mill, washing by deionized water, and drying to obtain the nano magnesium-lithium alloy.
5. The lithium battery anode composite material as claimed in claim 1, wherein the lanthanum copper aluminate is prepared by the following method: adding copper nitrate, lanthanum nitrate and aluminum nitrate into ethylene glycol, stirring and mixing uniformly, dropwise adding NaOH solution to adjust the pH value, continuously stirring for 30-60min, transferring into a polytetrafluoroethylene inner container, placing into a stainless steel hot reaction kettle, sealing, placing into a drying oven for reacting for 12-24h at the temperature of 150 ℃ and 170 ℃, cooling, removing the supernatant, washing a solid product with deionized water, and drying to obtain the lanthanum copper aluminate.
6. The lithium battery anode composite material as recited in claim 5, wherein the ratio of the amounts of the copper nitrate, the lanthanum nitrate and the aluminum nitrate is 3: 1: (3-5).
7. The lithium battery anode composite material as recited in claim 5, wherein the NaOH solution has a concentration of 3 to 5 mol/L; the pH value is adjusted to 9-10; the volume ratio of the total mass of the copper nitrate, the lanthanum nitrate and the aluminum nitrate to the glycol is (7-9): 50.
8. a method for preparing an anode composite for a lithium battery as claimed in any one of claims 1 to 7, comprising the steps of:
and grinding graphite to below 200 meshes, fully mixing the graphite with the nano magnesium-lithium alloy and the lanthanum copper aluminate, grinding by using a planetary ball mill, drying and tabletting to obtain the lithium battery anode composite material.
9. The preparation method as claimed in claim 8, wherein the planetary ball mill rotates at a speed of 450-550r/min for a period of 1-3 h.
10. Use of a lithium battery anode composite material as claimed in any one of claims 1 to 7 for the preparation of an anode for a fast-charging lithium battery.
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CN118231631A (en) * | 2024-05-23 | 2024-06-21 | 紫金矿业新能源新材料科技(长沙)有限公司 | Graphene/lithium magnesium alloy composite negative electrode material and preparation method and application thereof |
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2020
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Publication number | Priority date | Publication date | Assignee | Title |
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CN118231631A (en) * | 2024-05-23 | 2024-06-21 | 紫金矿业新能源新材料科技(长沙)有限公司 | Graphene/lithium magnesium alloy composite negative electrode material and preparation method and application thereof |
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