CN107785537B - Novel lithium ion battery positive pole piece, application thereof and modification method of pole piece - Google Patents
Novel lithium ion battery positive pole piece, application thereof and modification method of pole piece Download PDFInfo
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Abstract
The invention discloses a novel lithium ion battery anode pole piece, an application thereof and a pole piece modification method, wherein the method comprises the following steps: step 1, preparing a modified pole piece: coating the slurry containing the first material on one side of the aluminum foil to form a first coating, and drying to obtain a modified pole piece; step 2, coating the slurry containing the positive electrode active material on the first coating of the modified pole piece to form a second coating, and drying to obtain the modified positive pole piece of the lithium ion battery; wherein the first material has a lower operating voltage plateau than the positive active material. The modification method is simple and convenient to operate, universal and easy to industrialize. The lithium ion battery assembled by the modified positive pole piece can shorten the transmission path of lithium ions/electrons in the charging and discharging process, reduce the interface impedance, and bring higher charging and discharging efficiency, higher discharging specific capacity and excellent rate capability.
Description
Technical Field
The invention belongs to the field of electrochemistry, relates to a preparation method of a battery anode, and particularly relates to a method for modifying a lithium ion battery anode piece.
Background
With the development of economy and society, energy shortage has become a serious problem facing countries all over the world, which has prompted the continuous search of new environmental protection energy sources. Compared with the traditional cadmium-nickel and hydrogen-nickel batteries, the lithium ion battery has the advantages of high specific energy, high working voltage, wide application temperature range, low self-discharge rate, long cycle life and the like, is widely applied to mobile phones, notebook computers and other portable electrical appliances, and gradually expands the fields of high-power systems such as electric vehicles, smart power grids, satellites, distributed energy systems and the like.
From The current Development situation at home and abroad, countries in The world also propose medium and long term Development plans for high specific Energy chemical Energy storage power sources, for example, NASA (National Aeronautics and Space Administration, united states National aviation and Space navigation agency) and The farrow aeronautical battery manufacturer software company and The like determine The specific Energy target of a recent lithium ion battery to be 250-300 Wh/kg, and The Energy density of an Energy type lithium ion battery reaches 250Wh/kg in 2020 year in The Development plan of an electric vehicle power battery of japanese NEDO (The New Energy and Industrial Technology Development Organization, japan New Energy and Industrial Technology integrated Development Organization).
However, the energy density of lithium ion batteries is mainly limited by the positive electrode material, since the specific capacity of the commercial negative electrode carbon material is about 300-350 mAh/g, and the common positive electrode material (including LiCoO)2、LiNiO2Spinel-type LiMn2O4Layered LiMnO2、LiFePO4、Li[Ni1/3Co1/3Mn1/3]O2Etc.) has a specific capacity of 120 to 165 mAh/g,far below the theoretical capacity of the anode material.
With the continuous development of social economy and the rapid rise of other industries, the market still needs to be marketed with energy storage power supplies with higher performance, and the selection of electrode materials in the energy storage power supplies is the key point for determining the performance of the energy storage power supplies. The extreme imbalance of capacity development of the anode material and the cathode material in the electrode material seriously limits the rapid development of the high-specific-energy storage power supply, so that the development of the lithium ion battery anode material with higher capacity and better performance is vital from the aspects of material preparation, material optimization, battery design, preparation process and the like.
Disclosure of Invention
The invention aims to solve the problem of low specific capacity of the conventional lithium ion anode material, modify and modify the anode material of the lithium ion battery and improve the electrochemical properties of the anode material of the lithium ion battery, such as charge-discharge efficiency, specific discharge capacity and rate capability.
In order to achieve the purpose, the invention provides a novel method for modifying a positive pole piece of a lithium ion battery, which comprises the following steps:
step 1, preparing a modified pole piece: coating the slurry containing the first material on one side of the aluminum foil to form a first coating, and drying to obtain a modified pole piece;
step 2, coating the slurry containing the positive electrode active material on the first coating of the modified pole piece to form a second coating, and drying to obtain the modified positive pole piece of the lithium ion battery;
wherein the first material has a lower operating voltage plateau than the positive active material.
Preferably, the first material is selected from any one or a mixture of more than two of graphene, elemental sulfur, lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate.
Preferably, the positive active material is selected from any one or a mixture of more than two of lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, lithium-rich manganese-based material and lithium nickel manganese.
Preferably, the thickness of the first coating is 1 μm to 10 μm.
Preferably, the thickness of the second coating is 10 μm to 100 μm.
The invention also provides a lithium ion battery positive pole piece prepared by the modification method, which comprises a current collector, wherein the current collector is composed of an aluminum foil and a first coating coated on one side of the aluminum foil, the first coating is further coated with a second coating, the first coating comprises a first material, the second coating comprises an active material, and the working voltage platform of the first material is lower than that of the positive active material.
The invention also provides an application of the lithium ion battery positive pole piece prepared by the modification method, wherein the positive pole piece is used for the lithium ion battery.
The invention has the following advantages: the lithium ion battery assembled by the modified positive pole piece can shorten the transmission path of lithium ions/electrons in the charging and discharging process, reduce the interface impedance, and bring higher charging and discharging efficiency, higher discharging specific capacity and excellent rate capability. For example, the discharge specific capacity of the nickel cobalt lithium aluminate electrode modified by lithium iron phosphate at 0.1C can reach 194.6mAh/g, while the discharge specific capacity of the electrode without modification is only 184.6 mAh/g; the specific discharge capacity of the modified electrode at 5C can reach 150.2mAh/g, and the specific discharge capacity of the unmodified electrode is only 136.2 mAh/g. The method for modifying the positive pole piece of the lithium ion battery has universality and is also suitable for engineering application.
Drawings
Fig. 1 is a first charge-discharge curve of a lithium ion battery using the modified electrode sheet prepared in example 1 of the present invention as a positive electrode.
Fig. 2 is a rate performance curve of a lithium ion battery using the modified pole piece prepared in example 1 of the present invention as a positive electrode.
Fig. 3 is an impedance curve before cycle of a lithium ion battery using the modified electrode sheet prepared in example 1 of the present invention as a positive electrode.
Fig. 4 is a first charge-discharge curve of a lithium ion battery using the modified electrode sheet prepared in example 2 of the present invention as a positive electrode.
FIG. 5 is an SEM scanning electron micrograph of the modified positive electrode plate prepared in example 3 of the present invention.
Fig. 6 is a first charge-discharge curve of a lithium ion battery using the modified electrode sheet prepared in example 3 of the present invention as a positive electrode.
Fig. 7 is a first charge-discharge curve of a lithium ion battery using the modified electrode sheet prepared in example 4 of the present invention as a positive electrode.
Detailed Description
The invention provides a novel method for modifying a positive pole piece of a lithium ion battery, which comprises the following steps:
step 1, preparing a modified pole piece: coating the slurry containing the first material on one side of the aluminum foil to form a first coating, and drying to obtain a modified pole piece;
step 2, coating the slurry containing the positive electrode active material on the first coating of the modified pole piece to form a second coating, and drying to obtain the modified positive pole piece of the lithium ion battery;
wherein the first material has a lower operating voltage plateau than the positive active material.
The first material is selected from any one or a mixture of more than two of graphene, elemental sulfur, lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt manganate and lithium nickel cobalt aluminate.
The positive active material is any one or a mixture of more than two of lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, a lithium-rich manganese-based material and lithium nickel manganese oxide.
The thickness of the first coating is 1-10 mu m.
The thickness of the second coating is 10-100 mu m.
The dosage ratio of the first material to the positive active material is realized by adjusting the thicknesses of the first coating layer and the second coating layer.
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
Example 1
(1) Weighing a lithium iron phosphate material (LiFeP) according to a mass ratio of 8:1:1O4LFP), a conductive agent and an adhesive, wherein NMP (N-Methyl pyrrolidone) is used as a solvent for wet mixing, coated on an aluminum foil, and dried to obtain a pole piece with one side of the aluminum foil containing a low-voltage anode material as a modified pole piece; the conductive agent is acetylene black, and the binder is PVDF (Polyvinylidene Fluoride);
(2) weighing positive active material nickel cobalt lithium aluminate (LiNi) according to the mass ratio of 8:1:10.8Co0.15Al0.05O2NCA), a conductive agent and a binder, and obtaining anode slurry after wet mixing by taking NMP as a solvent;
(3) and (3) taking the modified pole piece prepared in the step (1) as a current collector, coating a layer of the positive electrode slurry prepared in the step (2) on the surface of the modified pole piece, and drying to obtain the modified positive pole piece Al-LFP-NCA of the lithium ion battery.
Wherein, one side of the aluminum foil contains a coating of a low-voltage anode material, and the thickness is 5 μm.
And a coating layer of the positive active material having a thickness of 50 μm.
The first charge-discharge curve of the lithium ion battery using the modified electrode plate prepared in this example 1 as the positive electrode is shown in fig. 1, and the battery is charged and discharged with a current of 0.1C, and it can be seen that the first specific discharge capacity of the battery using the Al-LFP-NCA modified positive electrode is 194.6mAh/g, which is higher than 184.6mAh/g of the Al-NCA unmodified electrode. The first coulomb efficiency of the battery adopting the modified anode is 85.0 percent and is higher than 81.6 percent of that of the unmodified electrode.
The rate performance curve of the lithium ion battery using the modified electrode sheet prepared in this example 1 as the positive electrode is shown in fig. 2, and it can be seen that the battery using the Al-LFP-NCA modified positive electrode has a specific discharge capacity of 150.2mAh/g at 5C high rate current, which is higher than 136.2mAh/g of the Al-NCA unmodified electrode.
An impedance diagram of the lithium ion battery using the modified pole piece prepared in the embodiment 1 as the positive electrode before circulation is shown in fig. 3, and it can be seen that the battery using the Al-LFP-NCA modified positive electrode has a smaller impedance value, which is more beneficial to the transmission of ions and electrons.
Example 2
(1) Weighing graphene materials (GR), a conductive agent and a binder according to a mass ratio of 8:1:1, mixing the graphene materials, the conductive agent and the binder by taking NMP as a solvent through a wet method, coating the mixture on an aluminum foil, and drying the mixture to obtain a pole piece with one side of the aluminum foil containing a low-voltage positive electrode material as a modified pole piece; the conductive agent is acetylene black, and the binder is PVDF (polyvinylidene fluoride);
(2) weighing positive active material nickel cobalt lithium aluminate (LiNi) according to the mass ratio of 8:1:10.8Co0.15Al0.05O2NCA), a conductive agent and a binder, and obtaining anode slurry after wet mixing by taking NMP as a solvent;
(3) and (3) taking the modified pole piece prepared in the step (1) as a current collector, coating a layer of the positive electrode slurry prepared in the step (2) on the surface of the modified pole piece, and drying to obtain the modified positive pole piece Al-GR-NCA of the lithium ion battery.
One side of the aluminum foil contained a coating of low voltage positive electrode material with a thickness of 5 μm.
And a coating layer of the positive active material having a thickness of 50 μm.
The electrochemical performance test result of the lithium ion battery modified positive pole piece Al-GR-NCA is shown in figure 4, and the battery is charged and discharged by 0.1C current, so that the specific discharge capacity of the battery adopting the Al-GR-NCA modified positive pole is 197.6mAh/g, which is higher than 184.6mAh/g of the Al-NCA unmodified electrode. Meanwhile, the discharge specific capacity of the battery with the Al-GR-NCA modified anode is 165.7mAh/g under the 2C multiplying power, which is higher than 148.7mAh/g of the battery with the Al-NCA unmodified electrode. The method for modifying the pole piece obviously improves the capacity performance and the rate capability of the raw materials.
Example 3
(1) Weighing a sulfur material (S), a conductive agent and a binder according to a mass ratio of 8:1:1, mixing by using NMP as a solvent through a wet method, coating the mixture on an aluminum foil, and drying to obtain a pole piece with one side of the aluminum foil containing a low-voltage positive electrode material as a modified pole piece; the conductive agent is acetylene black, and the binder is PVDF (polyvinylidene fluoride);
(2) weighing lithium iron phosphate (LiFePO) serving as positive electrode active material according to the mass ratio of 8:1:14LFP), conductive agent and adhesive, wet mixing with NMP as solventObtaining positive electrode slurry;
(3) and (3) taking the modified pole piece prepared in the step (1) as a current collector, coating a layer of the positive electrode slurry prepared in the step (2) on the surface of the modified pole piece, and drying to obtain the modified positive pole piece Al-S-LFP of the lithium ion battery.
One side of the aluminum foil contained a coating of low voltage positive electrode material with a thickness of 5 μm.
And a coating layer of the positive active material having a thickness of 100 μm.
An SEM image of the modified positive electrode sheet prepared in this example 3 is shown in fig. 5, and it can be seen that the small-particle lithium iron phosphate active material covers the surface of the sulfur material.
The first charge-discharge curve of the lithium ion battery using the modified electrode plate prepared in this example 3 as the positive electrode is shown in fig. 6, the charge-discharge is performed with a current of 0.1C, and the first specific discharge capacity of the battery using the Al-S-LFP modified positive electrode is 247.2 mAh/g.
Example 4:
(1) weighing lithium iron phosphate material (LiFePO) according to the ratio of 8:1:14LFP), conductive agent and adhesive, NMP is used as solvent to be mixed by wet method, coated on the aluminum foil, and dried to obtain a pole piece with one side of the aluminum foil containing low-voltage anode material as a modified pole piece; the conductive agent is acetylene black, and the binder is PVDF (polyvinylidene fluoride);
(2) weighing positive active material nickel cobalt lithium aluminate (LiNi) according to a ratio of 8:1:10.8Co0.15Al0.05O2NCA), a conductive agent and a binder, and obtaining anode slurry after wet mixing by taking NMP as a solvent;
(3) and (3) taking the modified pole piece prepared in the step (1) as a current collector, coating a layer of the positive electrode slurry prepared in the step (2) on the surface of the modified pole piece, and drying to obtain the modified positive pole piece Al-LFP-NCA of the lithium ion battery.
One side of the aluminum foil contained a coating of low voltage positive electrode material with a thickness of 2 μm.
And a coating layer of the positive active material having a thickness of 10 μm.
The electrochemical performance test result of the lithium ion battery modified positive pole piece Al-LFP-NCA is shown in figure 7, and the battery is charged and discharged by 0.1C current, so that the specific discharge capacity of the battery adopting the Al-LFP-NCA modified positive pole is 190.6mAh/g, which is higher than 184.6mAh/g of the Al-NCA unmodified electrode.
In summary, according to the modification method for the positive electrode plate of the lithium ion battery provided by the invention, the low-voltage material with the working voltage platform lower than that of the positive active material is coated on the aluminum foil, the modified electrode plate is used as a current collector, and then a layer of the positive active material of the lithium ion battery is coated on the surface of the modified electrode plate. The lithium ion battery assembled by the modified positive pole piece can shorten the transmission path of lithium ions/electrons in the charging and discharging process due to the existence of the step potential, reduce the interface impedance, and bring higher charging and discharging efficiency, higher discharging specific capacity and excellent rate capability. The capacity and the first effect of the modified electrode obtained in each embodiment are higher than those of an unmodified electrode, so that the electrochemical performance of the anode of the lithium ion battery is effectively improved.
In addition, the modification method of the lithium ion battery positive pole piece has universality and a simple preparation method, and is suitable for engineering application.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (7)
1. A novel method for modifying a positive pole piece of a lithium ion battery is characterized by comprising the following steps:
step 1, preparing a modified pole piece: coating the slurry containing the first material on one side of the aluminum foil to form a first coating, and drying to obtain a modified pole piece;
step 2, coating the slurry containing the positive electrode active material on the first coating of the modified pole piece to form a second coating, and drying to obtain the modified positive pole piece of the lithium ion battery;
the positive active material is any one or a mixture of more than two of lithium cobaltate, lithium manganate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, a lithium-rich manganese-based material and lithium nickel manganese oxide; the working voltage platform of the first material is lower than that of the positive active material, and any one or a mixture of more than two of elemental sulfur, lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate is selected.
2. The novel method for modifying the positive electrode plate of the lithium ion battery as claimed in claim 1, wherein the thickness of the first coating is 1 μm to 10 μm.
3. The novel method for modifying the positive electrode plate of the lithium ion battery as claimed in claim 1, wherein the thickness of the second coating is 10 μm to 100 μm.
4. The lithium ion battery positive electrode plate prepared by the modification method according to any one of claims 1 to 3, wherein the positive electrode plate comprises a current collector, the current collector is composed of an aluminum foil and a first coating coated on one side of the aluminum foil, a second coating is further coated on the first coating, the first coating comprises a first material, the second coating comprises an active material, and the working voltage platform of the first material is lower than that of the positive electrode active material.
5. The positive electrode plate of the lithium ion battery of claim 4, wherein the first material is selected from one or a mixture of more than two of elemental sulfur, lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt manganate and lithium nickel cobalt aluminate.
6. The positive electrode plate of the lithium ion battery of claim 4, wherein the positive active material is selected from any one or a mixture of more than two of lithium cobaltate, lithium manganate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, lithium rich manganese based material and lithium nickel manganese.
7. Use of the positive electrode plate of the lithium ion battery prepared by the modification method according to any one of claims 1 to 3, wherein the positive electrode plate is used for the lithium ion battery.
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| CN109560249A (en) * | 2018-11-30 | 2019-04-02 | 中国科学院过程工程研究所 | A kind of double-layer structure anode pole piece, and its preparation method and application |
| CN112751074B (en) * | 2019-10-29 | 2022-06-10 | 北京小米移动软件有限公司 | Lithium ion battery, preparation method thereof and electronic equipment |
| CN111554879A (en) * | 2020-05-11 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Positive plate, manufacturing method of positive plate and battery |
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