CN115863660A - Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof - Google Patents
Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 51
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011889 copper foil Substances 0.000 claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
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- 238000004519 manufacturing process Methods 0.000 claims 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
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- 101150058243 Lipf gene Proteins 0.000 description 3
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- 229910052782 aluminium Inorganic materials 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention relates to a negative current collector of a non-negative lithium battery and a preparation method and application thereof, belonging to the technical field of lithium batteries. The negative current collector of the non-negative lithium battery comprises a copper foil and a silver nano material generated in situ on the surface of the copper foil. And is prepared by the following method: carrying out oxidation treatment on the copper foil to generate CuO on the surface of the copper foil in situ; heating the oxidized copper foil to thermally decompose CuO into Cu 2 O; and soaking the copper foil after the heating treatment into a silver source solution, and preparing a silver nano material on the surface of the copper foil in situ by using a wet chemical method, namely the negative current collector. According to the invention, the lithium-philic silver nanowire is generated in situ on the copper foil, so that lithium ions can be induced to be uniformly deposited on the surface of the current collector, and the generation of lithium dendrites is further inhibited, thereby improving the safety performance and prolonging the service life of the lithium battery.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a negative electrode current collector of a non-negative lithium battery and a preparation method and application thereof.
Background
With the development and progress of society, the energy density of lithium ion batteries has not been satisfactory for peopleThe need for birth and life, and therefore, the search for battery technology with higher energy density is required. The theoretical specific capacity of the graphite cathode in the traditional lithium ion battery is only 372mAh/g, while the theoretical specific capacity of the lithium metal cathode is as high as 3860mAh/g, and in addition, the lithium metal also has lower density (0.59 g/cm) 3 ) And a lower electrochemical potential (-3.04V vs. standard hydrogen potential). Lithium metal batteries are therefore considered as the most promising new battery technology for replacing lithium ion batteries.
To realize a lithium metal battery with higher energy density, a lithium metal-free, non-negative electrode lithium battery represents one of the most advanced technologies in the field of lithium metal batteries. During the first charge of the battery, lithium from the positive electrode is deposited on the negative current collector. However, due to the lithium-phobic nature of commercial copper foil, the interaction between copper and lithium is weak, which results in non-uniform lithium deposition. Uncontrolled lithium deposition can form dendrites, deteriorate performance, and lead to safety concerns.
In the prior art, the technical problem of dendritic crystal formation of a lithium metal battery is solved by the following method: 1, coating a silver composite material on the surface of a metal foil for lithium precipitation, or coating metal silver in a negative electrode substrate for inhibiting the growth of metal lithium dendrites, wherein the materials can only be realized by coating, sputtering and coating, so that the weight and thickness of a pole piece are inevitably increased, and the improvement of capacity and density is not facilitated; meanwhile, the coating needs homogenate, and impurities are easy to introduce and are complex; the cost is also greatly increased; the common metal silver has no induction effect and cannot play the induction effect of uniform deposition of lithium. 2, the metal nanowires are transferred to the surface of the lithium foil through the template, the preparation method has complex steps, and uniform deposition of lithium cannot be really achieved, so that the energy density improvement is limited, and the prepared material cannot be directly used for a lithium battery without a negative electrode.
Disclosure of Invention
In order to solve the technical problems, the invention provides a negative current collector of a non-negative lithium battery, and a preparation method and application thereof. According to the invention, the lithium-philic silver nanowire is generated in situ on the copper foil, and has stronger affinity performance to lithium ions, so that the silver nanowire generated in situ can induce lithium ions to be uniformly deposited on the surface of the copper foil in the process of depositing the negative current collector by the lithium ions, thereby effectively preventing lithium dendrite from being generated, further enhancing the uniformity of lithium ion deposition, and further improving the safety performance and energy density of a battery cell.
The invention provides a negative current collector of a non-negative lithium battery, which comprises a copper foil and a silver nano material generated in situ on the surface of the copper foil.
In one embodiment of the present invention, the copper foil has a thickness of 4 to 10um. Further, preferably 5um to 10um; further, the preferable range is 6um to 10um; further, the preferable range is 7um to 10um; further, preferably 5um to 8um; further, it is preferably 6 to 8um. For example: 4um to 5um, 5um to 6um, 6um to 7um, 7um to 8um, 8um to 9um, 9um to 10um.
In one embodiment of the present invention, the silver nanomaterial is one or more of silver nanowires, silver nanofibers, and silver nanoparticles. Further, silver nanowires are preferable.
In one embodiment of the present invention, the silver nano material is silver nanowire, and the following conditions are met:
the length of the silver nanowire is 5-300 um; the diameter of the silver nanowire is 20 nm-500 nm.
Further, the length of the silver nanowire is 5-200 um; the diameter of the silver nanowire is 50 nm-200 nm. Further, the length of the silver nanowire is 10 um-100um, 20um-100um, 100um-200 um; the diameters of the silver nanowires are 50 nm-100nm, 100nm-200nm, 300nm-400nm and 400nm-500 nm.
The second object of the present invention is to provide a method for preparing the negative electrode current collector, comprising the steps of:
(1) Carrying out oxidation treatment on the copper foil to enable the surface of the copper foil to generate CuO in situ;
(2) And (2) heating the copper foil subjected to oxidation treatment in the step (1) to thermally decompose CuO into Cu 2 O and oxygen;
(3) Soaking the copper foil subjected to the heating treatment in the step (2) into a silver source solution, and preparing the copper foil in situ on the surface by using a wet chemical methodSilver nanomaterial, namely the negative electrode current collector. Wherein Cu is utilized in the wet chemical method 2 And O is used as a reducing agent and a structure directing agent, so that the silver nano material is uniformly generated on the surface of the copper foil in situ.
In one embodiment of the present invention, in the step (1), the oxidation treatment is performed by thermal oxidation.
In one embodiment of the invention, the temperature of the heating oxidation is 400-650 ℃. Further, it is preferably 400 to 500 ℃,500 to 600 ℃,600 to 650 ℃.
In one embodiment of the present invention, in the step (2), the temperature of the addition treatment is 950 to 1050 ℃. Further, the preferable temperature is 950 ℃ to 1000 ℃,1000 ℃ to 1050 ℃; for example: 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃,1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃ and the like.
In one embodiment of the present invention, in step (2), the heating treatment is performed under an inert gas atmosphere.
In one embodiment of the invention, the inert gas is selected from argon and/or nitrogen.
In one embodiment of the invention, in step (3), the silver source in the silver source solution is selected from soluble silver salts, such as AgNO 3 One or more of silver fluoride and silver perchlorate. The solvent of the silver source solution is water, ethylene glycol or propylene glycol.
In one embodiment of the present invention, in the step (3), the concentration of the silver source solution is 0.02mol/L to 0.07mol/L. Further, it is preferably 0.02mol/L to 0.05mol/L; for example: 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, etc.
In one embodiment of the present invention, in the step (3), the wet chemical method is a hydrothermal method or a solvothermal method.
In one embodiment of the present invention, in the step (3), the reaction temperature of the wet chemical method is 95 ℃ to 105 ℃. Further, the preferable temperature is 95-100 ℃, 100-105 ℃; for example: 95 deg.C, 96 deg.C, 97 deg.C, 98 deg.C, 99 deg.C, 100 deg.C, 101 deg.C, 102 deg.C, 103 deg.C, 104 deg.C, 105 deg.C, etc.
The third object of the invention is to provide a battery cell, which comprises the negative current collector of the non-negative lithium battery.
The fourth purpose of the invention is to provide a lithium battery, which comprises the battery cell.
The invention in-situ generation process of the lithium-philic silver nanowire comprises the following steps: cu (copper) 2 O as a reducing agent in Cu 2 The O site reduces silver ions into silver metal small particles, the initially reduced silver metal small particles become nucleation, the small particles slowly aggregate into large particles, and the large particles form a uniform linear body. Thus Cu 2 The site and reduction of O is critical in the in situ growth process.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the method can induce lithium ions to be uniformly deposited on the surface of a current collector by generating the lithium-philic silver nanowires on the copper foil in situ, and further inhibit the generation of lithium dendrites, thereby improving the safety performance and prolonging the service life of the lithium battery; meanwhile, the power performance of the lithium battery is improved by using the strong-conductivity silver nanowires generated in situ.
2, the invention avoids the operation of coating and homogenizing by in-situ growth, thereby reducing the introduction of impurities, simplifying the preparation process and greatly reducing the cost.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a graph showing cycle curves of lithium batteries obtained in example 1 of the present invention and comparative examples 1 to 2.
Fig. 2 is a scanning electron microscope image of in-situ generation of silver nanowires on the surface of the copper foil in example 1 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
The embodiment is a design of a negative current collector and a battery cell of a non-negative lithium battery, and specifically comprises the following steps:
(1) Commercial lithium iron phosphate is used as a positive electrode material, and the weight ratio of an active material lithium iron phosphate, a conductive agent SP and a binder PVDF is 97:2:1 in NMP solvent to form uniform positive electrode slurry, then coating the slurry on commercial 10 mu m aluminum foil, and drying to obtain the positive electrode plate.
(2) Commercial 4.5 μm copper foil was used as the negative current collector for the non-negative lithium battery. Oxidizing the copper foil at 500 ℃, and oxidizing the surface of the copper foil to produce CuO; heating the oxidized copper foil under the protection of Ar gas at 1000 ℃, and decomposing CuO on the surface of the copper foil by heating to generate Cu 2 O and oxygen; soaking the copper foil after heat treatment to 0.02mol/L AgNO 3 Heating to 100 deg.C in water solution, cu 2 And O is used as a reducing agent and a structure directing agent to generate silver nanowires on the surface of the copper foil in situ, as shown in figure 2. And taking the prepared copper foil with the in-situ grown silver nanowires as a negative current collector of the lithium battery without the negative electrode.
(3) Commercial 9 μ M thick PE membranes and 1M LiPF were used 6 The electrolyte (wherein the solvents are EC, DEC and DMC, and the volume ratio is 1.
Comparative example 1
The present comparative example provides a design scheme of a conventional lithium ion battery, and the difference from example 1 is that a negative electrode plate is adopted in step (2), specifically as follows:
(1) Commercial lithium iron phosphate is used as a positive electrode material, and an active material lithium iron phosphate, a conductive agent SP and a binder PVDF are mixed according to the weight ratio of 97:2:1 in NMP solvent to form uniform positive electrode slurry, then coating the slurry on commercial 10 mu m aluminum foil, and drying to obtain the positive electrode plate.
(2) Using commercial graphite as a negative electrode material, mixing graphite active material graphite, a conductive agent SP and a binder PVDF in a weight ratio of 97:1:2 in the weight ratio of the mixture to the aqueous solvent to form uniform negative electrode slurry, and then coating the slurry on a commercial 4.5 mu m copper foil and drying to obtain the negative electrode pole piece.
(3) Commercial 9 μ M thick PE membranes and 1M LiPF were used 6 The electrolyte (wherein the solvents are EC, DEC and DMC, and the volume ratio is 1.
Comparative example 2
The comparative example is a design scheme of a non-negative lithium battery, and is different from example 1 in that the negative current collector in step (2) is a commercial copper foil.
(1) Commercial lithium iron phosphate is used as a positive electrode material, and an active material lithium iron phosphate, a conductive agent SP and a binder PVDF are mixed according to the weight ratio of 97:2:1 in NMP solvent to form uniform positive electrode slurry, then coating the slurry on commercial 10 mu m aluminum foil, and drying to obtain the positive electrode plate.
(2) Commercial 4.5 μm copper foil was used as the negative current collector for the non-negative lithium battery.
(3) Commercial 9 μ M thick PE membranes and 1M LiPF were used 6 The electrolyte (wherein, the solvents are EC, DEC and DMC, the volume ratio is 1.
And (3) performance testing:
the lithium batteries obtained in example 1 and comparative examples 1 to 2 were subjected to weighing, capacity testing and cycle testing, and the test structures are shown in table 1 and fig. 1. Among them, the positive electrodes of example 1 and comparative examples 1 to 2 were designed at the same loading amount. (Capacity test and cycle test methods are all conventional test methods in the field)
Comparative example 1 is a conventional lithium battery system design, and since the SEI film generation of the graphite negative electrode consumes active lithium, the actual capacity is lower than that of comparative example 2 and example 1, the energy density is very low, and the cycle performance is superior.
Comparative example 2 and example 1 are designed for a lithium battery without a negative electrode, wherein in the comparative example 2, because the copper foil is not subjected to other treatment, lithium dendrite is generated in the circulation process, so that the circulation performance is deteriorated, the capacity retention rate is only 89% after 200 circles, and the water-skipping tendency is severe.
3, in example 1, the design of the battery using the negative electrode current collector of the non-negative lithium battery is shown, the weight of the battery cell is slightly increased by in-situ growing silver nano-wires on the surface of the copper foil, the overall energy density is far higher than that of comparative example 1, and the capacity retention rate of example 1 keeps the level of the prior art. The reason is as follows: the uniform silver nanowires growing on the copper foil in situ play a role in inducing lithium deposition, so that lithium is more uniformly deposited on the surface of the current collector, the generation of lithium dendrites is greatly inhibited, and the cycle performance of the battery is further greatly improved.
TABLE 1
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The negative current collector of the negative-electrode-free lithium battery is characterized by comprising a copper foil and a silver nano material generated on the surface of the copper foil in situ.
2. The negative electrode current collector of claim 1, wherein the copper foil has a thickness of 4 to 10um.
3. The negative electrode current collector of claim 1, wherein the silver nanomaterial is one or more of silver nanowires, silver nanofibers, and silver nanoparticles.
4. The negative electrode current collector of claim 3, wherein the silver nanomaterial is silver nanowires, subject to the following conditions:
the length of the silver nanowire is 5-300 um;
the diameter of the silver nanowire is 20 nm-500 nm.
5. The method of preparing a negative electrode current collector according to any one of claims 1 to 4, comprising the steps of:
(1) Carrying out oxidation treatment on the copper foil to enable the surface of the copper foil to generate CuO in situ;
(2) And (2) carrying out heating treatment on the copper foil subjected to the oxidation treatment in the step (1) to ensure that CuO is thermally decomposed into Cu 2 O；
(3) And (3) soaking the copper foil subjected to the heating treatment in the step (2) into a silver source solution, and preparing a silver nano material on the surface of the copper foil in situ by using a wet chemical method, namely the negative electrode current collector.
6. The production method according to claim 5, wherein in the step (1), the oxidation treatment is carried out by heating oxidation at a temperature of 400 to 650 ℃.
7. The production method according to claim 5, wherein the temperature of the heat treatment in the step (2) is 950 to 1050 ℃.
8. The production method according to claim 5, wherein in the step (3), at least one of the following conditions is satisfied:
the silver source in the silver source solution is soluble silver salt;
the concentration of the silver source solution is 0.02 mol/L-0.07 mol/L;
the wet chemical method adopts a hydrothermal method or a solvothermal method;
the heating temperature of the hydrothermal method or the solvothermal method is 95-105 ℃.
9. A cell comprising the negative current collector of the non-negative lithium battery of claims 1-4.
10. A lithium battery comprising the cell of claim 9.
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| CN117070945A (en) * | 2023-10-16 | 2023-11-17 | 瑞浦兰钧能源股份有限公司 | Copper foil and preparation method thereof |
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| CN117070945B (en) * | 2023-10-16 | 2024-02-06 | 瑞浦兰钧能源股份有限公司 | Copper foil and preparation method thereof |
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