CN113871593A - Ag-Cu2O-RGO lithium ion battery cathode material and preparation method thereof - Google Patents
Ag-Cu2O-RGO lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN113871593A CN113871593A CN202111130406.8A CN202111130406A CN113871593A CN 113871593 A CN113871593 A CN 113871593A CN 202111130406 A CN202111130406 A CN 202111130406A CN 113871593 A CN113871593 A CN 113871593A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 239000010406 cathode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 229910017944 Ag—Cu Inorganic materials 0.000 claims description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 5
- 238000005580 one pot reaction Methods 0.000 claims description 5
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 claims 1
- 101710134784 Agnoprotein Proteins 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004873 anchoring Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 44
- 239000000843 powder Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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Abstract
The invention discloses Ag-Cu2The invention relates to an O-RGO lithium ion battery cathode material and a preparation method thereof2O is used for controlling the shape, and simultaneously, the metal silver nano particles are introduced, and the shape is controlled by a simple potWater bath method, preparing to obtain Ag-Cu2The O-RGO composite material is used for testing various physical properties and electrochemical electrodes, battery performance and the like. The invention can obtain the lithium ion battery cathode material with high stability by simple operation steps and mild reaction conditions, carries out surface modification by anchoring silver nanoparticles, and utilizes the Fermi level of the metallic silver material and Cu2The overlapping of the conduction bands of the O electrode enhances the flow of electrons, so that Ag-Cu2The O-RGO negative electrode material has good cycle performance.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery electrode materials, and particularly relates to Ag-Cu2An O-RGO lithium ion battery cathode material and a preparation method thereof.
Background
In order to meet the increasing energy demand of human beings, especially the electric automobile market which is developed vigorously in recent years, it is important to develop new generation Lithium Ion Batteries (LIBs) having excellent performance. At present, commercial lithium ion batteries mainly adopt carbon materials such as artificial graphite and the like as a negative electrode, but due to low theoretical capacity (372mAh/g), the limitations of the traditional electrode materials in the aspects of specific capacity, cycle life and safety are increasingly prominent, and the further development of the lithium ion batteries is restricted.
In recent years, transition metal oxide materials have been developed into a novel lithium ion battery negative electrode material due to their high specific capacity, high energy density and unique phase transition lithium storage mechanism. Wherein cuprous oxide (Cu)2O) has been widely studied and applied in LIBs due to its advantages of high natural abundance, low cost, environmental friendliness, ease of synthesis, and the like. However, the inevitable large volume (over 228%) expansion associated with the lithiation/delithiation process easily leads to Cu2O electrode material powdering, leading to rapid capacity fade during cycling, and, in addition, Cu2The practical application of O in LIBs is also limited by its poor cycling stability due to low electronic conductivity.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to provide a Cu-Cu alloy2The O-modified high-performance lithium ion battery cathode material is prepared by a simple one-pot water bath method through Ag nano-particle growthIn Cu2Surface of O crystal, Ag-Cu2Construction of ternary Ag-Cu by loading of O with RGO nanosheets2An O-RGO composite material. The structure of the cathode material is reasonably designed and optimized to prepare the ternary composite material, and RGO and Ag-Cu are exerted by depending on the lithium storage mechanism of each component2And the improvement of chemical lithium storage is realized by the synergistic effect of O, so that the technical problem is solved, and the performance of the lithium ion battery is further improved.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
Ag-Cu2The O-RGO lithium ion battery cathode material is ternary Ag-Cu prepared by adopting a one-pot water bath method2O-RGO composite material, the ternary Ag-Cu2The O-RGO composite material is formed by growing Ag nano particles on Cu2Surface of O crystal, Ag-Cu2A structure in which O is supported by RGO nanosheets.
The Ag-Cu2The preparation method of the O-RGO lithium ion battery cathode material comprises the following steps:
the method comprises the following steps: under the condition of constant-temperature water bath, polyvinylpyrrolidone (PVP) and C are added6H5Na3O7·2H2O and Cu (NO)3)2·3H2Dissolving O in a Graphene Oxide (GO) aqueous solution;
step two: dropwise adding NaOH aqueous solution into the solution, and uniformly stirring to obtain a mixed solution I;
step three: adding disodium ethylene diamine tetraacetate (Na) dropwise into the mixed solution I2EDTA) water solution, and continuously stirring the mixture evenly to obtain a mixed solution II;
step four: mixing AgNO3Adding the aqueous solution into the second mixed solution, uniformly stirring, centrifuging the obtained mixed solution, washing with distilled water and ethanol for several times, drying in a vacuum drying oven, and finally preparing the Ag-Cu2The O-RGO composite material is used as the negative electrode material of the lithium ion battery.
In the first step, the temperature of the constant-temperature water bath is 35-75 ℃, and PVP and C are added6H5Na3O7·2H2O and Cu (NO)3)2·3H2The mass ratio of O is (6-10): (0.05-0.15): 0.1-0.3 g, and the O is dissolved in 50-100 mL of graphene oxide GO aqueous solution, and the concentration of the graphene oxide GO aqueous solution is 2 mg/mL.
The temperature of the constant-temperature water bath in the first step is 35-75 ℃.
And in the second step, the concentration of the NaOH aqueous solution is 2mol/L, 5-15 mL of the NaOH aqueous solution is added, and the stirring time is 20-40 min.
Na in step three2The concentration of the EDTA aqueous solution is 0.6mol/L, 5-15 mL of EDTA aqueous solution is added, and the stirring time is 1.5-3.5 h.
Step four the AgNO3Adding 10-30 mL of aqueous solution with the concentration of 5mmol/L, stirring for 20-40 min, centrifuging at the rotating speed of more than 6000rpm for 20-40 min, and vacuum drying the solid-phase precipitate obtained by centrifuging at the temperature of 60-70 ℃ for more than 10h to obtain Ag-Cu2O-RGO solid powder.
The method takes graphene oxide as a carrier, copper nitrate trihydrate as a precursor, and polyvinylpyrrolidone selectively adsorbs Cu on the surface2O is used for controlling the shape, and simultaneously, metal silver nano particles are introduced to prepare the Ag-Cu through a simple one-pot water bath method2The O-RGO composite material is used for testing various physical properties and electrochemical electrodes, battery performance and the like. The invention can obtain the lithium ion battery cathode material with high stability by simple operation steps and mild reaction conditions, carries out surface modification by anchoring silver nanoparticles, and utilizes the Fermi level of the metallic silver material and Cu2The overlapping of the conduction bands of the O electrode enhances the flow of electrons, so that Ag-Cu2The O-RGO negative electrode material has good cycle performance. Compared with the prior art, the invention has the following advantages:
1. the good electrochemistry of the battery cathode material is attributed to RGO and Ag-Cu2The synergistic effect of O, the RGO coating not only provides a three-dimensional conductive network, but also can be used as an active material for lithium storage; Ag-Cu2O supports multiple layers of RGO as the core skeleton and avoids the agglomeration of GO. The three-dimensional mesh of the RGO itself becomes Ag-Cu2The point of attachment of O greatly suppresses Cu2O lithium ion storageThe volume change in the process, the surface contact area between the electrode and the electrolyte is increased, the lithium ion diffusion distance is shortened, and the migration speed of electrons in the active material is accelerated.
2. The existence of the metal Ag nano particles enables the electrochemistry of the negative electrode material to be obviously improved. On the one hand improve Cu2The electric contact state among the O particles improves the utilization rate of the electroactive substances, and is beneficial to improving the capacity and the cycle performance; on the other hand, metallic Ag nanoparticles couple Li formed during the first discharge2The decomposition of O has high catalytic activity, reduces the generation of dead lithium and improves the reversible capacity.
3. The invention adopts a simple one-pot water bath method and adopts Na2EDTA as reducing agent, reducing graphite oxide to prepare RGO, and preparing Ag-Cu in one step2O-RGO composites exhibiting Ag nanoparticles grown in Cu2Surface of O crystal, Ag-Cu2The ternary composite structure with O supported by the RGO nanosheets has the advantages of stable structure, difficulty in agglomeration, large specific surface area, good processability and the like, can obviously improve the contact area of the negative electrode material and electrolyte, increase electrode reaction sites, increase the transmission rate of lithium ions and improve the coulombic efficiency and the rate capability of the negative electrode material.
PVP Cu adsorption by selective adsorption on the surface2O shape control and deposition on RGO to form Cu2O-RGO. Morphology and crystallinity of the particles for Cu2The electrochemical properties of O play an important role.
5. The Ag-Cu prepared by the invention2The O-RGO composite material as the lithium ion battery cathode material exerts the advantages of multiple components, utilizes the synergistic effect among the components, shows excellent rate performance, and has good application prospect in the field of the lithium ion battery cathode material.
Drawings
FIG. 1 shows Ag-Cu prepared in example 1 of the present invention2Scanning electron micrographs of O-RGO material.
FIG. 2 shows Ag-Cu prepared in example 1 of the present invention2X-ray diffraction patterns of O-RGO materials.
FIG. 3 shows Ag-Cu prepared in example 1 of the present invention2Graph of rate performance for O-RGO materials.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: under the condition of constant temperature water bath at 55 ℃, 8g of PVP and 0.1g of C are added6H5Na3O7·2H2O and 0.2g Cu (NO)3)2·3H2Dissolving O in 75mL of GO aqueous solution, wherein the concentration of GO is 2 mg/Ml;
step two: dropwise adding 10mL of NaOH solution (2mol/L) into the solution, and stirring for 30min to obtain a mixed solution I;
step three: after the mixture is uniformly stirred, 10mL of Na is dropwise added into the mixed solution I2-EDTA solution (0.6mol/L), and stirring for 2.5h to obtain a second mixed solution;
step four: 20mL of AgNO3Adding the solution (5mmol/L) into the second mixed solution, stirring for 30min, centrifuging the obtained mixed solution at 7000rpm for 30min, repeatedly washing with distilled water and ethanol to obtain powder solid, vacuum drying in a vacuum drying oven at 60 deg.C for 12 hr, and finally preparing Ag-Cu2An O-RGO composite material.
FIG. 1 shows Ag-Cu prepared in this example2Scanning electron micrographs of O-RGO material. It can be seen that Ag nanoparticles are grown in Cu2Surface of O crystal, Ag-Cu2And O is loaded by RGO nano sheets to construct the ternary composite material.
FIG. 2 shows Ag-Cu prepared in this example2X-ray diffraction pattern of O-RGO composite material. It can be seen that Ag-Cu2Cu in O-RGO composite2The phase structure of O is cubic phase (JCPDS No.05-0667), which is in contrast to Cu2The crystal phase structure of O is completely consistent, indicating that the loading of RGO does not affect Cu2Crystal structure of O.
FIG. 3 shows the present exampleAg-Cu prepared by examples2Graph of rate performance for O-RGO materials. Circulating for 10 circles under different current densities, returning to 0.2 and 0.1A/g after the current densities are 0.1, 0.2, 0.5, 1, 2 and 5A/g, and testing the cycle reversibility of the material, as can be seen from figure 3, Ag-Cu2The O-RGO material shows excellent rate performance, particularly, the negative electrode material can be basically recovered to the initial charge-discharge capacity after being recovered to the low-current charge-discharge after being charged and discharged by large current, and the Ag-Cu material shows that2The O-RGO material has good circulation reversibility.
Example 2
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: under the condition of constant temperature water bath at 35 ℃, 6g of PVP and 0.05g C6H5Na3O7·2H2O and 0.1g Cu (NO)3)2·3H2O is dissolved in 50mL of GO water solution, and the concentration of GO is 2 mg/mL;
step two: dropwise adding 5mL of NaOH solution (2mol/L) into the solution, and stirring for 20min to obtain a first mixed solution;
step three: after the mixture is uniformly stirred, 5mL of Na is dropwise added into the mixed solution I2-EDTA solution (0.6mol/L), and stirring for 1.5h to obtain a second mixed solution;
step four: 10mL of AgNO3Adding the solution (5mmol/L) into the second mixed solution, stirring for 20min, centrifuging the obtained mixed solution at 7000rpm for 20min, repeatedly washing with distilled water and ethanol to obtain powder solid, vacuum drying in a vacuum drying oven at 60 deg.C for 10 hr, and finally preparing Ag-Cu2An O-RGO composite material.
Example 3
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: under the condition of constant temperature water bath at 75 ℃, 10g of PVP and 0.15g C6H5Na3O7·2H2O and 0.3g Cu (NO)3)2·3H2O dissolved in 100mLIn the GO aqueous solution, the concentration of GO is 2 mg/mL;
step two: dropwise adding 15mL of NaOH solution (2mol/L) into the solution, and stirring for 40min to obtain a first mixed solution;
step three: after the mixture is uniformly stirred, 15mL of Na is dropwise added into the mixed solution I2-EDTA solution (0.6mol/L), and stirring for 3.5h to obtain a second mixed solution;
step four: 30mL of AgNO3Adding the solution (5mmol/L) into the second mixed solution, stirring for 40min, centrifuging the obtained mixed solution at 7000rpm for 40min, repeatedly washing with distilled water and ethanol to obtain powder solid, vacuum drying at 70 deg.C for 12h in vacuum drying oven, and finally preparing Ag-Cu2An O-RGO composite material.
Example 4
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: under the condition of constant temperature water bath at 75 ℃, 6g of PVP and 0.05g C6H5Na3O7·2H2O and 0.1g Cu (NO)3)2·3H2O is dissolved in 100mL of GO water solution, and the concentration of GO is 2 mg/mL;
step two: dropwise adding 5mL of NaOH solution (2mol/L) into the solution, and stirring for 20min to obtain a first mixed solution;
step three: after the mixture is uniformly stirred, 5mL of Na is dropwise added into the mixed solution I2-EDTA solution (0.6mol/L), and stirring for 1.5h to obtain a second mixed solution;
step four: 30mL of AgNO3Adding the solution (5mmol/L) into the second mixed solution, stirring for 40min, centrifuging the obtained mixed solution at 7000rpm for 30min, repeatedly washing with distilled water and ethanol to obtain powder solid, vacuum drying in a vacuum drying oven at 60 deg.C for 12 hr, and finally preparing Ag-Cu2An O-RGO composite material.
Example 5
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: under the condition of constant temperature water bath at 35 ℃, 10g of PVP and 0.15g C6H5Na3O7·2H2O and 0.3g Cu (NO)3)2·3H2O is dissolved in 50mL of GO water solution, and the concentration of GO is 2 mg/mL;
step two: dropwise adding 15mL of NaOH solution (2mol/L) into the solution, and stirring for 40min to obtain a first mixed solution;
step three: after the mixture is uniformly stirred, 15mL of Na is dropwise added into the mixed solution I2-EDTA solution (0.6mol/L), and stirring for 3.5h to obtain a second mixed solution;
step four: 10mL of AgNO3Adding the solution (5mmol/L) into the second mixed solution, stirring for 20min, centrifuging the obtained mixed solution at 7000rpm for 30min, repeatedly washing with distilled water and ethanol to obtain powder solid, vacuum drying at 70 deg.C for 12h in vacuum drying oven, and finally preparing Ag-Cu2An O-RGO composite material.
Example 6
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
the method comprises the following steps: under the condition of constant temperature water bath at 55 ℃, 8g of PVP and 0.1g C6H5Na3O7·2H2O and 0.2g Cu (NO)3)2·3H2O is dissolved in 100mL of GO water solution, and the concentration of GO is 2 mg/mL;
step two: dropwise adding 10mL of NaOH solution (2mol/L) into the solution, and stirring for 30min to obtain a mixed solution I;
step three: after the mixture is uniformly stirred, 10mL of Na is dropwise added into the mixed solution I2-EDTA solution (0.6mol/L), and stirring for 2.5h to obtain a second mixed solution;
step four: 30mL of AgNO3Adding the solution (5mmol/L) into the second mixed solution, stirring for 40min, centrifuging at 7000rpm for 30min, and repeatedly washing with distilled water and ethanol to obtain the final productThe obtained powder solid is put into a vacuum drying oven to be dried for 12 hours in vacuum at the constant temperature of 70 ℃, and finally the Ag-Cu is obtained2An O-RGO composite material.
Claims (8)
1. Ag-Cu2The O-RGO lithium ion battery cathode material is characterized in that the ternary Ag-Cu material is prepared by adopting a one-pot water bath method2O-RGO composite material, the ternary Ag-Cu2The O-RGO composite material is formed by growing Ag nano particles on Cu2Surface of O crystal, Ag-Cu2A structure in which O is supported by RGO nanosheets.
2. An Ag-Cu alloy according to claim 12The preparation method of the O-RGO lithium ion battery cathode material is characterized by comprising the following steps:
the method comprises the following steps: under the condition of constant-temperature water bath, polyvinylpyrrolidone and C are added6H5Na3O7·2H2O and Cu (NO)3)2·3H2Dissolving O in the graphene oxide aqueous solution;
step two: dropwise adding NaOH aqueous solution into the solution, and uniformly stirring to obtain a mixed solution I;
step three: dropwise adding an ethylene diamine tetraacetic acid disodium solution into the mixed solution I, and continuously stirring uniformly to obtain a mixed solution II;
step four: mixing AgNO3Adding the aqueous solution into the second mixed solution, stirring uniformly, centrifuging the obtained mixed solution, washing with distilled water and ethanol for several times, drying in a vacuum drying oven, and finally preparing the Ag-Cu2The O-RGO composite material is used as the negative electrode material of the lithium ion battery.
3. Ag-Cu according to claim 22The preparation method of the O-RGO lithium ion battery cathode material is characterized in that polyvinylpyrrolidone and C are added in the step one6H5Na3O7·2H2O and Cu (NO)3)2·3H2The mass ratio of O is (6-10): (0.05-0.15): (0.1-0.3) g, dissolved in 50-100 mLIn the graphene oxide aqueous solution, the concentration of the graphene oxide aqueous solution is 2 mg/mL.
4. Ag-Cu according to claim 22The preparation method of the O-RGO lithium ion battery cathode material is characterized in that the temperature of the constant-temperature water bath in the step one is 35-75 ℃.
5. Ag-Cu according to claim 22The preparation method of the O-RGO lithium ion battery cathode material is characterized in that in the second step, the NaOH aqueous solution with the concentration of 2mol/L is added into the mixture in an amount of 5-15 mL, and the stirring time is 20-40 min.
6. Ag-Cu according to claim 22The preparation method of the O-RGO lithium ion battery cathode material is characterized in that the concentration of the disodium ethylene diamine tetraacetate aqueous solution in the third step is 0.6mol/L, 5-15 mL of disodium ethylene diamine tetraacetate aqueous solution is added, and the stirring time is 1.5-3.5 h.
7. Ag-Cu according to claim 22The preparation method of the O-RGO lithium ion battery cathode material is characterized in that the AgNO is prepared in the fourth step3The concentration of the aqueous solution is 5mmol/L, 10-30 mL of the aqueous solution is added, and the stirring time is 20-40 min.
8. Ag-Cu according to claim 22The preparation method of the O-RGO lithium ion battery cathode material is characterized in that in the fourth step, the rotating speed of centrifugation is more than 6000rpm, the centrifugation time is 20-40 min, and the solid-phase precipitate obtained by centrifugation is dried for more than 10h in vacuum at the temperature of 60-70 ℃ to prepare Ag-Cu2An O-RGO composite material.
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