CN114552032B - Manufacturing and using method of positive electrode pre-lithiation additive of lithium ion energy storage device - Google Patents
Manufacturing and using method of positive electrode pre-lithiation additive of lithium ion energy storage device Download PDFInfo
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- CN114552032B CN114552032B CN202210143959.5A CN202210143959A CN114552032B CN 114552032 B CN114552032 B CN 114552032B CN 202210143959 A CN202210143959 A CN 202210143959A CN 114552032 B CN114552032 B CN 114552032B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention provides a pre-lithiation material taking stable aluminum-lithium alloy powder as a positive electrode of a lithium ion energy storage device, a preparation process and a use method thereof. The positive electrode pre-lithiation material is aluminum-lithium binary alloy powder, and the main structural formula is Al x Li y Wherein x is more than 1 and less than 4, and y is more than 1 and less than 9. The invention synthesizes the materials by adopting the traditional high-temperature solid-phase melting method, has simple preparation method and can be used for large-scale manufacture. The method applies the pre-lithiation reagent to the surface of the positive electrode plate of the lithium ion energy storage device by adopting a solution spraying method, and has the characteristic of compatibility with the traditional lithium ion battery production process. The pre-lithiation reagent is a cathode sacrificial alloy compound with excellent lithium contribution capability, good conductivity and strong chemical stability. The lithium ion energy storage device containing the positive electrode prelithiation agent aluminum-lithium alloy prepared by the method has the advantages of remarkably improved capacity, good cycling stability, capability of improving the energy density of the lithium ion energy storage device and good application prospect.
Description
Technical Field
The invention relates to the technical field of additives of lithium ion energy storage devices, in particular to a manufacturing and using method of a positive electrode pre-lithiation additive of a lithium ion energy storage device.
Background
Lithium ion batteries are an efficient and clean energy storage device, and have received much attention in recent years. The energy density is high, the memory effect is avoided, the self-discharge is small, and the like, so that the energy density is considered to be one of the most promising electrochemical energy storage systems. In order to meet the requirements of high-efficiency and complex social development, the development of high-energy density lithium ion batteries has become a common expectation of current manufacturers. For this reason, a great deal of work has been done on electrode materials to increase the energy density of the battery. However, high specific capacity materials tend to suffer from structural instability and poor initial coulombic efficiency. For example, silicon as a negative electrode material for lithium ion batteries has a theoretical specific capacity of 4200mAh/g, but its large volume expansion during the initial cycle consumes a large amount of lithium to generate an SEI film. This process is irreversible and reduces the overall battery capacity. The prelithiation technique may introduce excess lithium into the battery system to offset the significant lithium loss from the initial cycling. This is not only one of the keys to increase the energy density of current commercial lithium ion batteries, but also is a necessary way to realize the next generation lithium ion batteries.
Electrochemical prelithiation is a common prelithiation strategy, widely used in laboratory prelithiation. The pre-lithiation degree is precisely controlled by an external circuit through constructing a half-cell system of the anode material and the metallic lithium. However, after pre-lithiation, the half cell needs to be disassembled, the anode removed, and the complete cell rebuilt. The whole process has high environmental requirements, is complex to operate and is difficult to apply on a large scale. Stable Lithium Metal Powder (SLMP) can exist stably in dry air and is widely used for pre-lithiation of modern commercial batteries. The initial efficiency of the anode can be greatly improved by uniformly dispersing SLMP in an organic solvent and then coating the organic solvent on the anode electrode film. Positive electrode prelithiation strategies are also another effective way to supplement active lithium loss. By adding a sacrificial lithium salt such as (L i) to the positive electrode material 3 N、M/L i 2 CO 3 、M/Li 2 S, etc.) to supplement the first irreversible lithium consumption of the negative electrode.
Disclosure of Invention
In view of the above, in order to solve the above-mentioned shortcomings in the background art, on the one hand, the present invention provides a positive electrode prelithiation additive, which has high prelithiation capability and stable electrode characteristics.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a stable aluminum-lithium alloy material is used as a positive electrode pre-lithiation additive of a lithium ion energy storage device, a main material is aluminum-lithium alloy, and the material comprisesThe general formula of the alloy material is as follows: al (Al) x Li y Wherein x is more than 1 and less than 4, and y is more than 1 and less than 9.
On the other hand, the invention provides a preparation method of the stable aluminum-lithium alloy material as a positive electrode prelithiation additive of a lithium ion energy storage device, which comprises the following steps:
s1, in a dry environment with a dew point less than-40 ℃, metal aluminum and metal lithium are mixed according to the mass ratio (1-3): 1, uniformly mixing to form a metal mixture, and placing the metal mixture into an atmosphere furnace;
s2, heating the metal mixture to 185-200 ℃ in an inert atmosphere, preserving heat for 2-8h, then heating to 200-800 ℃ and preserving heat for 2-8h, and finally naturally cooling to room temperature to form an alloy block;
s3, grinding the alloy block into fine powder aluminum-lithium alloy powder with the particle size of (0.1-5 um) in an inert atmosphere;
and S4, heating the fine powder to 80 ℃ in a vacuum environment, preserving heat for 2 hours, and finally introducing dry air for annealing to obtain the aluminum-lithium alloy powder with stable passivation.
In still another aspect, the present invention further provides a method for using the stable aluminum lithium alloy material as a positive electrode prelithiation additive for a lithium ion energy storage device, comprising the steps of:
s1, uniformly mixing a lithium ion battery anode, a conductive agent, an adhesive and an aluminum lithium alloy, adding a certain amount of an organic solvent, and dispersing at high speed to form uniform slurry, wherein the organic solvent comprises one of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), tetrahydrofuran (THF) and dimethyl carbonate (DMC);
s2, uniformly dispersing the slurry on the surface of the positive electrode plate by a spraying mode or any other electrode forming technology to form a positive electrode plate containing passivated aluminum lithium alloy, wherein the addition amount is 0.1-50% of the mass of the positive electrode active substance;
s3, after the positive electrode plate containing the aluminum-lithium alloy is formed, manufacturing a lithium ion energy storage device according to a lithium ion battery forming technology, wherein the lithium ion energy storage device comprises a lithium ion battery, a lithium ion super capacitor or a lithium ion battery capacitor;
and S4, charging the energy storage device containing the stable aluminum-lithium alloy for the first time, and then releasing lithium in the aluminum-lithium alloy to achieve the aim of prelithiation.
Drawings
FIG. 1 is a schematic flow chart of the preparation of an aluminum-lithium alloy according to the present invention;
FIG. 2 is an X-ray diffraction and scanning electron microscope image of an aluminum lithium alloy of the present invention;
FIG. 3 is a graph showing the initial charge of a half cell composed of an aluminum lithium alloy and metallic lithium, which is a material of the present invention;
FIG. 4 is a graph showing the first charge and discharge curves of a half cell made from the aluminum-lithium alloy material of the present invention after addition to the surfaces of lithium cobaltate and ternary NCM622 electrode plates;
FIG. 5 is a plot of the first charge and discharge and cycle life of a ternary NCM 622/hard carbon full cell containing an aluminum lithium alloy material of the present invention;
fig. 6 is a schematic diagram of the mechanism of action of the aluminum lithium alloy material of the present invention in a full cell.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and the accompanying drawings. The following description is given of the present invention, but is not intended to limit the present invention to these descriptions.
Example 1
As shown in fig. 1, the aluminum-lithium alloy material of the present invention is mainly produced by a high-temperature melting reaction of metallic lithium and metallic aluminum. The specific method comprises the following steps: lithium foil and aluminum foil in different proportions are first stacked together in an environment with a relative humidity of less than 5%, then placed in a nickel crucible, and transferred to a tube furnace. The molten lithium metal may corrode the aluminum foil by heat treatment at 200 deg.c for 4 hours in an argon atmosphere. Heat treatment at 700 c for 4 hours can then melt both metals to form a more uniform aluminum lithium alloy. Finally, an aluminum lithium alloy powder is obtained by grinding, and then a stable aluminum lithium alloy powder is formed by dry air thermal annealing.
Example 2
Specific case consists of the aluminum/lithium metal weight ratio of example 1: 1:2.5,1:2,1:1.5. After it is preparedThe material detailed XRD data is shown in fig. 2 (b). The three proportions of aluminum-lithium alloy mainly comprises Al 4 L i 9 (PDF # 24-0008) phase, belonging to B2/m space group. With decreasing lithium content, al 4 Li 9 The phase gradually changes to Al L i (PDF#03-1215) phase. The XRD diffraction peaks of the three samples are sharp and clear, which shows that the material has good crystallinity.
As shown in the scanning electron microscope of FIG. 2 (c-d), the aluminum lithium alloy powder is formed by stacking a plurality of elliptic secondary particles, the surface roughness is like broccoli, and the particle size after grinding is 5-20 mu m.
Example 3
The aluminum lithium alloy powder (80%), carbon black (SP, 10%) and polyvinylidene fluoride (PVDF, 10%) of example 2 were uniformly mixed in different proportions. The above materials were uniformly dispersed in Tetrahydrofuran (THF) to form a slurry, which was then coated on an aluminum foil 20 μm thick. The aluminum lithium alloy positive electrode and the metal lithium negative electrode are assembled into a CR2032 coin half cell in a glove box with humidity and oxygen concentration of less than 1.0 ppm.
The half cell thus produced was then subjected to a charge-discharge test, the specific test results of which are shown in fig. 3. The specific capacity of the aluminum-lithium alloy increased with decreasing Al/L i ratio, but when the Al/Li ratio was decreased from 2.5 to 1.5, the specific capacity of the aluminum-lithium alloy was only from 922mAh g -1 Increasing to 966mAh g -1 . The poor capacity improvement may be due to L i and Al forming only a limited proportion of stable compounds, while excess lithium is not stable and provides capacity during later processing.
Example 4
And (3) spraying the slurry prepared from the aluminum-lithium alloy powder prepared in the embodiment 3 on the surface of the positive plate of the lithium ion battery according to the addition amounts of different proportions. The specific addition amount accounts for 1-4% of the total mass of the active material. Then preparing lithium cobaltate and ternary half-cell in glove box, and finally respectively charging and discharging at constant current in the potential range of 3.0-4.25V.
Specific charge and discharge data are shown in fig. 4, and charge and discharge curves of the original lithium cobaltate electrode and the lithium cobaltate electrode added with 2% of aluminum lithium alloy in a voltage range of 3-4.25V are shown in fig. 4 (a). Adding 2% aluminum lithium compared with the original electrodeThe initial charge capacity of the gold electrode is from 150mAh g -1 Increase to 171.26mAh g -1 。21.26mAh g -1 Is provided by an aluminum-lithium alloy, and is equivalent to the specific capacity of 1063mAh g -1 . However, both lithium cobaltate electrodes after initial charge completion showed similar discharge capacities, indicating that the aluminum lithium alloy had no negative effect on the electrodes after active lithium release.
We have added 4% aluminum lithium alloy to the NCM electrode surface to study its compatibility. As shown in FIG. 4 (b), the alloy containing 4% aluminum and lithium (224 mAh g -1 ) The specific capacity of the NCM electrode of (2) was higher than that of the original NCM (189 mAh g -1 ) The specific capacity is 875mAh g, which is increased by 18.5 percent and is equivalent to that provided by aluminum-lithium alloy -1 . The difference in electrode conductivity and material particle size may result in a lower specific capacity of the aluminum lithium alloy in the NCM electrode than in the lithium cobalt oxide electrode.
Example 5
This example is used to illustrate the compatibility of the aluminum lithium alloy prepared according to the present invention in a full cell. NCM/HC pouch cells are manufactured in an environment with a relative humidity of less than 10%. The cathode was NCM electrode containing an aluminum lithium alloy additive and the anode was HC. The 90% aluminum lithium alloy was mixed with 10% pvdf, then uniformly dispersed in THF, and finally sprayed onto the dried NCM electrode surface.
As shown in FIG. 5, the initial specific charge capacity of the original NCM full cell is 189mAh g -1 . However, it can be increased to 211mAh g by adding 2.5% aluminum lithium alloy separately -1 . The difference of the capacities is mainly represented on the marked places on the curve, and the extra capacity provided by the aluminum-lithium alloy is equivalent to 840-860mAh g -1 Is a specific capacity contribution of (c).
Fig. 6 shows the variation of the aluminum lithium alloy sacrificial material of the present invention across the surface of the positive electrode. The aluminum-lithium alloy applied to the surface of the positive electrode is converted into lithium ions and metallic aluminum under the induction of electric potential. Lithium ions move to the negative electrode under the action of voltage, and metallic lithium is remained at the positive electrode to stabilize the interface of the positive electrode. The stability of the battery is enhanced while the capacity of the lithium ion soft package battery is increased. The battery capacity is greatly improved from the view of a cycle curve, and the battery cycle stability is excellent.
Claims (3)
1. The utility model provides a lithium ion energy storage device anodal prelithiation additive stable aluminum lithium alloy material which characterized in that: the main material is aluminum lithium alloy, and the general formula of the alloy material is as follows: al (Al) x Li y Wherein x is more than 1 and less than 4, y is more than 1 and less than 9, and the surface of the main material contains Li 2 CO 3 、Li 2 O、Li 3 N and Al 2 O 3 Inert shell material.
2. A method of preparing the stabilized aluminum lithium alloy material of claim 1 as a positive pre-lithiation additive for a lithium ion energy storage device, comprising the steps of:
s1, in a dry environment with a dew point less than-40 ℃, metal aluminum and metal lithium are mixed according to the mass ratio (1-3): 1, uniformly mixing to form a metal mixture, and placing the metal mixture into an atmosphere furnace;
s2, heating the metal mixture to 185-200 ℃ in an inert atmosphere, preserving heat for 2-8h, then heating to 200-800 ℃ and preserving heat for 2-8h, and finally naturally cooling to room temperature to form an alloy block;
s3, grinding the alloy block into fine powder aluminum-lithium alloy powder with the particle size of (0.1-5 um) in an inert atmosphere;
and S4, heating the fine powder to 80 ℃ in a vacuum environment, preserving heat for 2 hours, and finally introducing dry air for annealing to obtain the aluminum-lithium alloy powder with stable passivation.
3. A method of using the stabilized aluminum lithium alloy material of claim 1 in a positive electrode prelithiation process for a lithium ion energy storage device, comprising the steps of:
s1, uniformly mixing a lithium ion battery anode, a conductive agent, an adhesive and an aluminum lithium alloy, adding a certain amount of an organic solvent, and dispersing at high speed to form uniform slurry, wherein the organic solvent comprises one or more of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), tetrahydrofuran (THF) and dimethyl carbonate (DMC);
s2, uniformly dispersing the slurry on the surface of the positive electrode plate by a spraying mode or any other electrode forming technology to form the positive electrode plate containing stable aluminum-lithium alloy, wherein the addition amount is 0.1-50% of the mass of the positive electrode active material;
s3, after the positive electrode plate containing the stable aluminum-lithium alloy is formed, manufacturing a lithium ion energy storage device according to a lithium ion battery forming technology, wherein the lithium ion energy storage device comprises a lithium ion battery, a lithium ion super capacitor or a lithium ion battery capacitor;
and S4, charging the energy storage device containing the stable aluminum-lithium alloy for the first time, and then releasing lithium in the aluminum-lithium alloy to achieve pre-lithiation.
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