Modified copper nanowire, and preparation method and application thereof

Abstract

The application discloses modified copper nanowires, a preparation method and application thereof. The modified copper nanowires comprise copper nanowires and a composite modifier distributed on the surface of the copper nanowires; the composite modifier comprises a compound with an amine group and a compound with an amino acid group; the molar ratio of the compound with the amine group to the compound with the amino acid group is (10-60):1; the compound with the amino acid group is connected to the surface of the copper nanowires through an amino group and / or a carboxyl group; and the compound with the amine group is connected to the surface of the copper nanowires through an amine group. The modified copper nanowires have high purity, a large aspect ratio, small diameter and uniform size, and excellent oxidation resistance.

Description

Technical Field

[0001] This invention relates to a modified copper nanowire, its preparation method, and its application. Background Technology

[0002] In recent years, copper nanomaterials have attracted much attention as a potential alternative to indium selenide (ITO), a transparent conductive film material. Copper nanowires, in particular, exhibit relatively lower sheet resistance compared to spherical copper nanoparticles (Cu NPs), making them more suitable as transparent electrode materials. However, copper nanomaterials are unstable in air and easily oxidized, which limits their widespread application. Therefore, preparing copper nanomaterials with excellent oxidation resistance is crucial to solving this problem.

[0003] Currently, most reported methods for preparing high-quality copper nanowires involve using long-chain amines such as oleylamine (OLA), octadecylamine (ODA), and hexadecylamine (HDA) as modifiers, employing liquid-phase reduction with a reducing agent. However, the copper nanowires obtained by this method need to be stored in hexane or hydrazine hydrate solution to prevent oxidation. This not only increases costs but also because hydrazine hydrate is toxic. Chinese patent documents CN103706785A and CN113996799A disclose a method for preparing copper nanomaterials using amino acids and their analogues as modifiers. Copper nanomaterials prepared using amino acids as modifiers exhibit excellent antioxidant properties, but cannot yield high-quality copper nanowires with a large aspect ratio.

[0004] Therefore, there is an urgent need to provide a copper nanowire that is not only of high quality and has a large aspect ratio, but also has excellent antioxidant properties. Summary of the Invention

[0005] To overcome the shortcomings of existing copper nanowires in which quality and antioxidant properties cannot be simultaneously achieved, this invention provides a modified copper nanowire, its preparation method, and its application. The modified copper nanowire of this invention has high purity, small diameter, uniform size, large aspect ratio, and excellent antioxidant properties.

[0006] The present invention solves the above-mentioned technical problems by adopting the following technical solutions:

[0007] This invention provides a modified copper nanowire, comprising copper nanowires and a composite modifier distributed on the surface of the copper nanowires; the composite modifier comprises a compound having an amino group and a compound having an amino acid group; the molar ratio of the compound having an amino group to the compound having an amino acid group is (10-60):1;

[0008] The compound having amino acid groups is attached to the surface of the copper nanowires via amino and / or carboxyl groups; the compound having amino groups is attached to the surface of the copper nanowires via amino groups.

[0009] In this invention, the molar ratio of the compound having an amino group to the compound having an amino acid group in the composite modifier is preferably (12-60):1, more preferably (20-60):1, for example 30:1, 37.5:1 or 40:1.

[0010] In this invention, the compound having an amino acid group can be conventional in the art, and is preferably one or more of lysine, serine, threonine, arginine, glycine and proline, for example, lysine or serine.

[0011] In this invention, the compound having an amino group can be an amine compound with a long carbon chain, preferably an amine compound with a carbon chain length of 6 or more, more preferably an amine compound with a carbon chain length of 12-18, such as oleylamine, hexadecylamine or octadecylamine.

[0012] Those skilled in the art will know that the ultrafine copper nanowires typically refer to copper nanowires with a diameter of 20-80 nm. In this invention, the diameter of the modified copper nanowires is preferably 30-43 nm, for example, 36 nm, 39 nm, or 40 nm.

[0013] In this invention, the length of the modified copper nanowire can be 100 μm or more, preferably 240-260 μm, for example 250 μm.

[0014] In this invention, the ratio of the length to the diameter of the modified copper nanowire is denoted as the aspect ratio, which can be 5000 or higher, preferably 5814-8333, for example 6000, 6046, 6500, 6667, 7222 or 8000.

[0015] The present invention also provides a method for preparing modified copper nanowires, which includes the following steps: subjecting copper salt, reducing agent, composite modifier and water to a hydrothermal reaction to obtain the modified copper nanowires.

[0016] The composite modifier includes a compound having an amino group and a compound having an amino acid group; the molar ratio of the compound having an amino group to the compound having an amino acid group is (10-60):1; the reducing agent is glucose or L-ascorbic acid.

[0017] The inventors of this invention have discovered through long-term research that by using compounds with amino acid groups and compounds with amine groups as modifiers, and glucose or L-ascorbic acid as reducing agents, and employing a hydrothermal reaction, high-quality modified copper nanowires with a large aspect ratio and excellent antioxidant properties can be obtained.

[0018] In this invention, the compound having an amino acid group can be conventional in the art, and is preferably one or more of lysine, serine, threonine, arginine, glycine and proline, for example, lysine or serine.

[0019] In this invention, the compound having an amino group can be an amine compound with a long carbon chain, preferably an amine compound with a carbon chain length of 6 or more, more preferably an amine compound with a carbon chain length of 12-18, such as oleylamine, hexadecylamine or octadecylamine.

[0020] In this invention, when the compound with an amino group is oleylamine and the compound with an amino acid group is lysine, the quality and yield of the modified copper nanowires obtained are both good.

[0021] In this invention, the molar ratio of the compound having an amino group to the compound having an amino acid group in the composite modifier is preferably (12-60):1, more preferably (20-60):1, for example 30:1, 37.5:1 or 40:1.

[0022] In this invention, the copper salt can be a conventional water-soluble inorganic acid copper salt or a hydrate of an inorganic acid copper salt.

[0023] The inorganic copper acid salt is preferably one or more of copper nitrate, copper sulfate, copper halide, and copper acetate.

[0024] The inorganic copper acid salt hydrate is preferably one or more of the hydrates of copper nitrate, copper sulfate, copper halide, and copper acetate, such as copper chloride dihydrate.

[0025] In this invention, the molar ratio of the reducing agent to the copper salt can be conventional in the art, preferably (0.1-200):1, more preferably (0.5-10):1, and even more preferably (1-5):1, for example 2:1, 4:1 or 4.5:1.

[0026] In this invention, the amount of water used can be conventional in the art, generally enough to completely dissolve the copper salt, the composite modifier and the reducing agent. Preferably, the mass ratio of water to copper salt is (100-500):1, more preferably (200-300):1, for example 254.9:1 or 235.3:1.

[0027] In this invention, the temperature of the hydrothermal reaction can be 100-200℃, more preferably 100-170℃, for example 120℃.

[0028] In this invention, the hydrothermal reaction time can be conventional in the art, generally 4-100h, preferably 8-48h, more preferably 10-24h, for example 18h, 20h or 22h.

[0029] In this invention, the hydrothermal reaction may further include stirring, the purpose of which is to mix the copper salt, the reducing agent, the composite modifier and the water evenly.

[0030] The stirring time can be 0-24 hours, preferably 2-10 hours.

[0031] In this invention, the hydrothermal reaction may further include a first separation, purification and drying step.

[0032] The purpose of the first separation is to separate the crude modified copper nanowire product from the reaction solution.

[0033] The first separation can be performed using conventional solid-liquid separation methods in the art, such as centrifugation.

[0034] The first separation preferably includes the following steps: washing the reaction solution obtained after the hydrothermal reaction with water and then centrifuging it.

[0035] The refining process can be carried out using methods conventional in the art, generally including washing, secondary separation, and filtration.

[0036] The purpose of the washing is to remove impurities from the modified copper nanowire product.

[0037] The detergent used for washing can be conventional in the art, preferably CHCl3.

[0038] The purpose of the second separation is to separate the impurities from the modified copper nanowires.

[0039] The second separation can be performed using conventional solid-liquid separation methods in the art, such as centrifugation.

[0040] The preferred filtration method is membrane filtration. The filter membrane used in the membrane filtration method can be conventional in the art, and is preferably an alumina membrane, cellulose ester membrane, nylon membrane, polyethersulfone membrane, polycarbonate membrane, polytetrafluoroethylene membrane, or polyvinylidene fluoride membrane.

[0041] The pore size of the filter membrane is preferably 0.2-0.45 μm, for example, 0.22 μm.

[0042] The drying process is preferably vacuum drying.

[0043] In a preferred embodiment of the present invention, the method for preparing the modified copper nanowires includes the following steps: subjecting copper salt, reducing agent, composite modifier and water to a hydrothermal reaction to obtain the modified copper nanowires.

[0044] The composite modifier comprises oleylamine and lysine; the molar ratio of oleylamine to lysine is (20-60):1;

[0045] The reducing agent is glucose or L-ascorbic acid; the copper salt is copper chloride dihydrate; the molar ratio of the reducing agent to the copper salt is (0.5-10):1;

[0046] The mass ratio of the water to the copper salt is (200-300):1;

[0047] The hydrothermal reaction temperature is 100-170℃; the hydrothermal reaction time is 10-24h.

[0048] The present invention also provides a modified copper nanowire, which is prepared by the modified copper nanowire preparation method described above.

[0049] The present invention also provides an application of the modified copper nanowires as described above in battery materials.

[0050] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0051] The reagents and raw materials used in this invention are all commercially available.

[0052] The positive and progressive effects of this invention are as follows:

[0053] (1) The modified copper nanowires of the present invention have high purity, small diameter and uniform size, large aspect ratio and excellent oxidation resistance.

[0054] (2) The method for preparing modified copper nanowires of the present invention uses water and anhydrous ethanol as media, does not require high concentration of alkali, has mild reaction conditions, and is environmentally friendly; and the reducing agent is a natural product, which is cheap and readily available; furthermore, the method for preparing modified copper nanowires of the present invention also has a high yield, all of which are higher than 68.4%, and the preferred embodiment is even higher than 90%. Attached Figure Description

[0055] Figure 1 This is a SEM image of the modified copper nanowires prepared in Example 1.

[0056] Figure 2 This is a SEM image of the modified copper nanowires prepared in Example 1.

[0057] Figure 3 This is a SEM image of the modified copper nanowires prepared in Example 4.

[0058] Figure 4 This is a SEM image of the modified copper nanowires prepared in Example 4.

[0059] Figure 5 This is a SEM image of the modified copper nanowires prepared in Example 5.

[0060] Figure 6 This is a SEM image of the modified copper nanowires prepared in Example 5.

[0061] Figure 7 This is a SEM image of the modified copper nanowires prepared in Comparative Example 1.

[0062] Figure 8 This is a SEM image of the modified copper nanowires prepared in Comparative Example 1.

[0063] Figure 9 This is a SEM image of the modified copper nanowires prepared in Comparative Example 2.

[0064] Figure 10 This is a SEM image of the modified copper nanowires prepared in Comparative Example 2.

[0065] Figure 11 This is a SEM image of the modified copper nanowires prepared in Comparative Example 3.

[0066] Figure 12 This is a SEM image of the modified copper nanowires prepared in Comparative Example 3.

[0067] Figure 13 The images show the XRD patterns of freshly modified copper nanowires prepared in Example 1 and modified copper nanowires stored in air for different numbers of days.

[0068] Figure 14 The images show the XRD patterns of freshly modified copper nanowires prepared in Comparative Example 1 and modified copper nanowires stored in air for different numbers of days.

[0069] Figure 15 XPS images of freshly modified copper nanowires prepared in Example 1 and modified copper nanowires stored in air at 139D.

[0070] Figure 16 XPS images of freshly prepared modified copper nanowires and modified copper nanowires stored in air with 139D, as shown in Comparative Example 1.

[0071] Figure 17 The image shows the micro-infrared spectrum of the modified copper nanowires prepared in Example 1. Detailed Implementation

[0072] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0073] In this embodiment of the invention, copper chloride dihydrate, glucose, L-ascorbic acid, lysine, oleylamine, hexadecylamine and serine were purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd., and octadecylamine was purchased from Beijing Innocare Technology Co., Ltd.

[0074] The FESEM field emission scanning electron microscope is model FEI Nova NanoSEM 450; the XRD diffractometer is model X'Pert Powder PAN alytical X. · The X-ray electron spectrometer (XPS) is model PHI-5000Versa Probe; the Fourier transform micro-infrared spectrometer is model Nicolet iN10.

[0075] Example 1

[0076] (1) Dissolve copper chloride dihydrate (0.51 g, 0.003 mol), glucose (0.54 g, 0.003 mol), and lysine (0.06 g, 0.0004 mol) in 130 mL of water to obtain mixed solution A;

[0077] (2) Mix oleylamine (6 mL, 0.018 mol) and 10 mL of anhydrous ethanol and stir until homogeneous to obtain mixed solution B. Add the mixed solution A obtained in step (1) to the mixed solution B under strong stirring and continue stirring for 10 h to obtain mixed solution C. The molar ratio of oleylamine to lysine is 45:1, the molar ratio of reducing agent to copper salt is 1:1, and the mass ratio of water to copper salt is 254.9:1.

[0078] (3) Transfer the mixed solution C to the hydration vessel and react at 120℃ for 24h to obtain the reaction solution; cool the reaction solution to room temperature and wash it with water, then centrifuge to obtain the crude copper nanowire product. Wash the crude copper nanowire product with CHCl3 and centrifuge it. Filter it with a microporous membrane with a diameter of 0.22μm and then vacuum dry it to obtain the modified copper nanowire.

[0079] Example 2

[0080] (1) Dissolve copper chloride dihydrate (0.51 g, 0.003 mol), glucose (0.54 g, 0.003 mol), and lysine (0.06 g, 0.0004 mol) in 120 mL of water to obtain mixed solution A;

[0081] (2) Mix the modifier oleylamine (5 mL, 0.015 mol) and 10 mL of anhydrous ethanol and stir until homogeneous to obtain mixed solution B. Add the mixed solution A obtained in step (1) to the mixed solution B under strong stirring and continue stirring for 2 h to obtain mixed solution C. The molar ratio of oleylamine to lysine is 37.5:1, the molar ratio of reducing agent to copper salt is 1:1, and the mass ratio of water to copper salt is 235.3:1.

[0082] (3) Transfer the mixed solution C to the hydration vessel and react at 120℃ for 20h to obtain the reaction solution; cool the reaction solution to room temperature and wash it with water, then centrifuge to obtain the crude copper nanowire product. Wash the crude copper nanowire product with CHCl3 and centrifuge it. Filter it with a microporous membrane with a diameter of 0.22μm and then vacuum dry to obtain the modified copper nanowire.

[0083] Example 3

[0084] (1) Dissolve copper chloride dihydrate (0.51 g, 0.003 mol), glucose (0.54 g, 0.003 mol), and lysine (0.09 g, 0.0006 mol) in 120 mL of water to obtain mixed solution A;

[0085] (2) Mix oleylamine (6 mL, 0.018 mol) and 10 mL of anhydrous ethanol and stir until homogeneous to obtain mixed solution B. Add the mixed solution A obtained in step (1) to the mixed solution B under strong stirring and continue stirring for 10 h to obtain mixed solution C. The molar ratio of oleylamine to lysine is 30:1, the molar ratio of reducing agent to copper salt is 1:1, and the mass ratio of water to copper salt is 235.3:1.

[0086] (3) Transfer the mixed solution C to the hydration vessel and react at 120℃ for 22h to obtain the reaction solution; cool the reaction solution to room temperature and wash it with water, then centrifuge to obtain the crude copper nanowire product. Wash the crude copper nanowire product with CHCl3 and centrifuge it. Filter it with a microporous membrane with a diameter of 0.22μm and then vacuum dry it to obtain the modified copper nanowire.

[0087] Example 4

[0088] (1) Dissolve copper chloride dihydrate (0.51 g, 0.003 mol), glucose (0.54 g, 0.003 mol), and serine (0.16 g, 0.0015 mol) in 120 mL of water to obtain mixed solution A;

[0089] (2) Mix oleylamine (6 mL, 0.018 mol) and 10 mL of anhydrous ethanol and stir until homogeneous to obtain mixed solution B. Add the mixed solution A obtained in step (1) to the mixed solution B under strong stirring and continue stirring for 10 h to obtain mixed solution C. The molar ratio of oleylamine to serine is 12:1, the molar ratio of reducing agent to copper salt is 1:1, and the mass ratio of water to copper salt is 235.3:1.

[0090] (3) Transfer the mixed solution C to the hydration vessel and react at 120℃ for 22h to obtain the reaction solution; cool the reaction solution to room temperature and wash it with water, centrifuge to obtain the crude copper nanowire product, then wash the crude copper nanowire product with CHCl3 and centrifuge to separate and purify it, filter it with a microporous membrane with a diameter of 0.22μm, and finally vacuum dry to obtain the modified copper nanowire.

[0091] Example 5

[0092] In this embodiment, in step (1), the reducing agent is L-ascorbic acid (0.53g, 0.003mol), and all other steps are the same as in Example 4.

[0093] Example 6

[0094] In this embodiment, in step (1), the reducing agent is L-ascorbic acid (0.27g, 0.0015mol), and all other steps are the same as in Example 4.

[0095] Example 7

[0096] In this embodiment, the modifier in step (2) is hexadecylamine (2.90g, 0.012mol), and all other steps are the same as in Example 1.

[0097] Example 8

[0098] In this embodiment, the modifier in step (2) is octadecylamine (3.23g, 0.012mol), the temperature is 180℃, and everything else is the same as in Example 1.

[0099] Comparative Example 1

[0100] In this comparative example, lysine was not added in step (1), and everything else was the same as in Example 1.

[0101] Comparative Example 2

[0102] In this comparative example, lysine (0.36 g, 0.0024 mol) was added in step (1); oleylamine (6 mL, 0.018 mol) was added in step (2). The molar ratio of oleylamine to lysine was 7.5:1. All other steps were the same as in Example 1.

[0103] Comparative Example 3

[0104] In this comparative example, serine (0.33 g, 0.003 mol) was added in step (1); oleylamine (6 mL, 0.018 mol) was added in step (2). The molar ratio of oleylamine to serine was 6:1. All other steps were the same as in Example 4.

[0105] Example 1

[0106] The modified copper nanowires prepared in Examples 1-8 and Comparative Examples 1-3 were characterized by SEM. The diameters of the modified copper nanowires prepared in Examples 1-8 and Comparative Examples 1-3 were also measured. Specifically, 80-110 modified copper nanowires were collected, their diameters were measured, and the average value was recorded as the diameter of the modified copper nanowire. The SEM images and diameter results are shown below. Figure 1-12 As shown in Table 1.

[0107] Table 1. Product parameters and yields of modified copper nanowires prepared in Examples 1-8 and Comparative Examples 1-3

[0108]

[0109]

[0110] As shown in Table 1, the modified copper nanowires prepared in Examples 1-8 are copper nanowires with large aspect ratios, with lengths between 240-260 μm, diameters between 30-43 nm, and aspect ratios between 5814-8333. Furthermore, combined with... Figure 1 and Figure 2 As can be seen, the modified copper nanowires prepared in Example 1 have high purity, uniform size, and high yield, which is above 68.4%. Figure 3 and Figure 4 This is a SEM image of the modified copper nanowires prepared in Example 4. Figure 5 and Figure 6 This is a SEM image of the modified copper nanowires prepared in Example 5. As can be seen from the image, the copper nanowires prepared in Examples 4 and 5 have a large aspect ratio, regular morphology, and uniform size.

[0111] Figure 7 and Figure 8 The image shows the SEM image of the modified copper nanowires prepared in Comparative Example 1, which uses oleylamine as a modifier. As can be seen from Table 1, the purity and yield of the modified copper nanowires in Examples 1-8 of this invention are comparable to or even better than those in Comparative Example 1.

[0112] Referring to Table 1, and comparing Example 1 and Comparative Examples 2-3, it can be seen that when the molar ratio of the compound with an amino group to the compound with an amino acid group in the composite modifier is less than 10:1, for example, the molar ratio of oleylamine to lysine in Comparative Example 2 is 7.5:1, and the molar ratio of oleylamine to serine in Comparative Example 3 is 6:1, the lengths of the modified copper nanowires obtained are 30 μm and 3.9 μm, and the diameters are 70 nm and 90 nm, respectively. Figure 9 and Figure 10 This is a SEM image of the modified copper nanowires prepared in Comparative Example 2. Figure 11 and Figure 12The image shows the SEM image of the modified copper nanowires prepared in Comparative Example 3. As can be seen, Comparative Example 2 contained a large number of nanoparticles, severely affecting the purity of the nanowires. The copper nanowires prepared in Comparative Example 3 were shorter in length, larger in diameter, and had a smaller aspect ratio; strictly speaking, they should be classified as nanorod structures. They also contained nanoparticles, and the yield was relatively low. Crucially, high-quality nanowires could not be guaranteed.

[0113] Example 2

[0114] The modified copper nanowires prepared in Example 1 and Comparative Example 1 were characterized by XRD to monitor their antioxidant properties. XRD characterization was performed on fresh modified copper nanowires and on modified copper nanowires stored in air for 4 days (4D), 7 days (7D), 28 days (28D), 49 days (49D), and 139 days (139D). The XRD patterns for different storage days are shown below. Figure 13 and Figure 14 As shown. The peak at 2θ = 36.9° (PDF#05-0667) in the XRD pattern corresponds to the characteristic diffraction peak of copper oxide. From Figure 13 and Figure 14 As can be seen, the modified copper nanowires prepared in Example 1 did not show characteristic diffraction peaks of copper oxide after 139 days, while the modified copper nanowires prepared in Comparative Example 1 showed obvious characteristic diffraction peaks of copper oxide after 139 days. This indicates that the modified copper nanowires prepared in Example 1 have better antioxidant capacity than the modified copper nanowires prepared in Comparative Example 1.

[0115] Example 3

[0116] XPS characterization was performed on the modified copper nanowires prepared in Example 1 and Comparative Example 1 to investigate their antioxidant properties. XPS characterization was performed on fresh modified copper nanowires and modified copper nanowires stored in air for 139 days, respectively. The results are as follows: Figure 15 and Figure 16 As shown, the peaks near 943.6 eV and 962.4 eV in the XPS spectrum correspond to the characteristic Cu 2p peak and satellite peak of copper oxide, respectively. From... Figure 15 and Figure 16 It can be seen that the modified copper nanowires prepared in Example 1 showed a weaker Cu 2p satellite peak of copper oxide after 139 days, while the modified copper nanowires prepared in Comparative Example 1 showed obvious Cu 2p characteristic peaks and satellite peaks of copper oxide after 139 days. This indicates that the modified copper nanowires prepared with amino acids and oleylamine as modifiers have better antioxidant capacity than the modified copper nanowires prepared with oleylamine as a modifier alone.

[0117] Example 4

[0118] The modified copper nanowires prepared in Example 1 were subjected to micro-infrared spectroscopy, and the results are as follows: Figure 17 As shown. At 3316cm -1 The nearby peak corresponds to the stretching vibration peak of -NH2, at 1732.6 cm⁻¹. -1 The nearby peak corresponds to the stretching vibration peak of C=O, at 1654.9 cm⁻¹. -1 The nearby peak corresponds to the stretching vibration peak of -COOH, indicating the presence of lysine on the surface of the modified copper nanowires; at 2922.0 cm⁻¹ -1 and 2852.6cm -1 The two strong stretching vibration peaks appearing nearby correspond to the stretching vibration peaks of -CH2-CH3, at 1457.8 cm⁻¹. -1 and 1375.9cm -1 The two peaks appearing nearby correspond to the variable-angle bending vibration peaks of -CH2-CH3, at 721.4 cm⁻¹. -1 The nearby peaks correspond to stretching vibrations of carbon chains with six or more carbons, indicating the presence of long-chain amines on the surface of the modified copper nanowires, at 3009.3 cm⁻¹. -1 The nearby peaks correspond to the stretching vibration peaks of C=C, which confirms the presence of oleylamine on the surface of the modified copper nanowires. The above results indicate that the modified copper nanowires are jointly modified by lysine and oleylamine.

[0119] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A modified copper nanowire, characterized in that, The modified copper nanowires include copper nanowires and a composite modifier distributed on the surface of the copper nanowires; the composite modifier includes a compound having an amino group and a compound having an amino acid group; the molar ratio of the compound having an amino group and the compound having an amino acid group is (20-60):1; the compound having an amino group is oleylamine, and the compound having an amino acid group is lysine; The compound having amino acid groups is attached to the surface of the copper nanowires via amino and / or carboxyl groups; the compound having amino groups is attached to the surface of the copper nanowires via amino groups. The modified copper nanowire has a diameter of 30-43 nm, and the ratio of the length to the diameter of the modified copper nanowire is denoted as the aspect ratio, which is ≥5000. The modified copper nanowires were prepared by the following method: The product is obtained by hydrothermal reaction of copper salt, reducing agent, composite modifier and water; The reducing agent is glucose, and the molar ratio of the reducing agent to the copper salt is (0.5-10):1; the mass ratio of the water to the copper salt is (200-300):

1. The copper salt is a water-soluble inorganic acid copper salt or a hydrate of an inorganic acid copper salt. The hydrate of the inorganic acid copper salt is one or more of copper nitrate, copper sulfate, and copper halide hydrates. The temperature of the hydrothermal reaction is 100-170℃.

2. The modified copper nanowires as described in claim 1, characterized in that, The molar ratio of the compound having an amino group to the compound having an amino acid group is 30:1, 37.5:1, or 40:

1.

3. The modified copper nanowires as described in claim 1, characterized in that, The length of the modified copper nanowires is 240-270 μm.

4. The modified copper nanowires as described in claim 3, characterized in that, The modified copper nanowires have a diameter of 36 nm, 39 nm, or 40 nm. And / or, the length of the modified copper nanowire is 250 μm, 253 μm, 260 μm or 265 μm.

5. A method for preparing the modified copper nanowires according to claim 1, characterized in that, It includes the following steps: a hydrothermal reaction of copper salt, reducing agent, composite modifier and water to obtain the product; The composite modifier includes a compound having an amino group and a compound having an amino acid group; the compound having an amino group is oleylamine, the compound having an amino acid group is lysine, and the molar ratio of the compound having an amino group to the compound having an amino acid group is (20-60):

1. The reducing agent is glucose, and the molar ratio of the reducing agent to the copper salt is (0.5-10):1; the mass ratio of water to the copper salt is (200-300):

1. The copper salt is a water-soluble inorganic acid copper salt or a hydrate of an inorganic acid copper salt. The hydrate of the inorganic acid copper salt is one or more of copper nitrate, copper sulfate, and copper halide hydrates. The temperature of the hydrothermal reaction is 100-170℃.

6. The method for preparing modified copper nanowires as described in claim 5, characterized in that, The molar ratio of the compound having an amino group to the compound having an amino acid group is 30:1, 37.5:1, or 40:

1.

7. The method for preparing modified copper nanowires as described in claim 6, characterized in that, The molar ratio of the reducing agent to the copper salt is (1-5):1; And / or, the mass ratio of the water to the copper salt is 254.9:1 or 235.3:

1.

8. The method for preparing modified copper nanowires as described in claim 7, characterized in that, The molar ratio of the reducing agent to the copper salt is 2:1, 4:1, or 4.5:

1.

9. The method for preparing modified copper nanowires as described in claim 8, characterized in that, The hydrate of the inorganic copper acid salt is copper chloride dihydrate.

10. The method for preparing modified copper nanowires as described in claim 5, characterized in that, The hydrothermal reaction time is 4-100 hours; And / or, the hydrothermal reaction is further performed by stirring for 0-24 hours.

11. The method for preparing modified copper nanowires as described in claim 10, characterized in that, The hydrothermal reaction time is 8-48 hours; And / or, the hydrothermal reaction is further preceded by stirring, the stirring time being 2-10 hours.

12. The method for preparing modified copper nanowires as described in claim 11, characterized in that, The temperature of the hydrothermal reaction is 120°C; And / or, the hydrothermal reaction time is 10-24 h.

13. The method for preparing modified copper nanowires as described in claim 12, characterized in that, The hydrothermal reaction time is 18h, 20h, or 22h.

14. The method for preparing modified copper nanowires as described in claim 5, characterized in that, After the hydrothermal reaction is completed, the process also includes a first separation, purification and drying step; The first separation method is centrifugation; The refining process includes washing, a second separation, and filtration. The filtration method is membrane filtration. The drying process is described as vacuum drying.

15. The method for preparing modified copper nanowires as described in claim 14, characterized in that, The detergent used for washing is CHCl3; The pore size of the filter membrane used in the membrane filtration method is 0.2-0.8 μm.

16. The method for preparing modified copper nanowires as described in claim 15, characterized in that, The filter membrane used in the membrane filtration method has a pore size of 0.22 μm.

17. The application of the modified copper nanowire as described in any one of claims 1-4 in battery materials.

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