CN110635103A - Flexible nano porous metal oxide cathode for secondary battery and preparation method thereof - Google Patents
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Abstract
A preparation method of a flexible nano porous metal oxide negative electrode for a secondary battery comprises the following steps: (1) preparing a composite sandwich structure alloy foil strip; (2) preparing flexible nano-porous alloy oxide: placing the alloy foil strip in ammonium sulfate for water bath dealloying to prepare flexible nano-porous alloy, taking out the alloy foil strip from absolute ethyl alcohol, placing the alloy foil strip in a ventilation position for self-propagating combustion, and generating a flexible nano-porous alloy oxide electrode; (3) preparing a defect nano porous alloy oxide electrode: the alloy oxide electrode rich in defects is prepared by selectively reducing oxides such as Cu. According to the flexible nano porous metal oxide cathode for the secondary battery and the preparation method thereof, disclosed by the invention, the nano porous metal is introduced into the cathode material for preparing the secondary battery in batches by self-propagating combustion for the first time, the process is simple, and the cost is low; spontaneous combustion can simultaneously cause rapid oxidation of the surface and coarsening of the pore structure, thereby generating the nano-porous integrated electrode with high active substance loading capacity.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a flexible nano porous metal oxide cathode for a secondary battery and a preparation method thereof.
Background
Secondary batteries are new types of energy storage devices currently in commercial use. Among them, the negative electrode material is one of the main factors affecting the performance of the secondary battery because of having a low discharge potential and a high theoretical specific capacity. In the traditional negative electrode material, the specific capacity per unit area of commercial graphite is generally lower than 3mAh cm-2And the practical application of the portable electronic product is seriously influenced. Transition metal oxides are highly valued for their high theoretical specific capacity. However, the transition metal oxide causes rapid deterioration of rate and stability due to defects such as poor conductivity and volume expansion during intercalation and deintercalation of lithium ions. The nanocrystallization of the material can provide a buffer space for the volume expansion of the material, and the introduction of the conductive reinforcement in the intrinsic active layer can effectively improve the defects, but the loading amount of the nanomaterial in the high-performance nanomaterial electrode prepared by the traditional method is too low (1-2mg cm)-2) Resulting in a lack of practical value.
In recent years, transition group metal oxides having a nanoporous structure have received a high degree of attention in the field of energy storage. The nano porous metal prepared by dealloying can be used as a current collector for a negative electrode of a lithium ion battery due to the advantages of good conductivity and high specific surface area. The nano porous metal is subjected to surface oxidation to prepare the metal @ oxide composite electrode. But due to the brittleness problem of the nano-porous metal, the integrated application is difficult to realize. Meanwhile, reasonable regulation and control of the integrated electrode are also key factors for improving the electrochemical performance of the integrated electrode. The introduction of a dopant phase or oxygen vacancies in the oxide layer improves poor conductivity and provides an effective buffer space for volume expansion during electrode charging and discharging.
Disclosure of Invention
In view of the above, the present invention is directed to a flexible nanoporous metal oxide negative electrode for a secondary battery and a method for preparing the same, so as to further prepare a high active material loading amount and combine high conductivity of a defective electrode and provide more ion active sites.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a flexible nano porous metal oxide negative electrode for a secondary battery comprises the following steps:
(1) preparing the alloy foil strip: polishing and grinding two NiCuMn alloys or two NiCoMn alloys with the thickness of 1cm, cleaning with alcohol, drying, then selecting Cu or Ni plates with the thickness of 1-2mm as an intermediate interlayer for symmetrical edge sealing and vacuum sheath welding, heating the wrapped and welded laminated plate to 600-1000 ℃, carrying out hot rolling after carrying out heat preservation for 30-120min, controlling the rolling amount to be within 30%, carrying out repeated rolling to obtain a plate with the thickness of 1mm, and carrying out repeated vacuum annealing and cold rolling on the plate to obtain an alloy foil belt with the thickness of 50-200 um;
(2) preparing flexible nano-porous alloy oxide: placing the alloy foil tape in 1mol/L ammonium sulfate, dealloying in a water bath at 60 ℃ to prepare a nano porous alloy, cleaning the nano porous alloy, directly taking out the cleaned nano porous alloy from absolute ethyl alcohol, placing the cleaned nano porous alloy in a ventilation position, and performing self-propagating combustion to generate a flexible nano porous alloy oxide electrode;
(3) preparing a defect nano porous alloy oxide electrode: and (3) placing the flexible nano-porous alloy oxide foil strip in a hydrogen furnace for annealing treatment to prepare the flexible nano-porous alloy oxide electrodes with different defect degrees and metal doping.
Further, in the step (1), in the NiCuMn alloy, the molar mass fraction of Mn is 60-70%, the molar mass fraction of Ni is 5-25%, and the balance is the molar mass fraction of Cu; the molar mass of Mn in the NiCoMn alloy is 60-70%, the molar mass of Ni is 5-25%, and the balance is the molar mass of Co.
Further, the alloy foil strip prepared in the step (1) is NiCuMn/Cu/NiCuMn alloy foil strip, NiCoMn/Cu/NiCoMn alloy foil strip, NiCuMn/Ni/NiCuMn alloy foil strip or NiCoMn/Ni/NiCoMn alloy foil strip.
Further, the temperature of the vacuum annealing in the step (1) is 600-800 ℃.
Further, the nano-porous alloy prepared in the step (2) is NiCuMn/Cu/NiCuMn nano-porous alloy, NiCoMn/Cu/NiCoMn nano-porous alloy, NiCuMn/Ni/NiCuMn nano-porous alloy or NiCoMn/Ni/NiCoMn nano-porous alloy.
Further, the annealing temperature in the step (3) is controlled to be 200-.
Further, the nano-porous metal is subjected to self-propagating combustion in the air atmosphere to prepare the low-energy-consumption oxide.
Further, the flexible nano porous metal oxide cathode prepared by the preparation method is applied to secondary batteries, wherein the secondary batteries comprise lithium ion batteries, sodium ion batteries and potassium ion batteries.
Compared with the prior art, the flexible nano porous metal oxide cathode for the secondary battery and the preparation method thereof have the following advantages:
(1) the nano porous metal self-propagating combustion is introduced into the batch preparation of the negative electrode material for the lithium ion battery for the first time, the preparation process is simple, and the cost is low;
(2) spontaneous combustion can cause rapid oxidation of the surface and coarsening of the pore structure, resulting in a highly active material loaded nanoporous integrated electrode (> 7mg cm)-2);
(3) In the annealing treatment of dealloying, spontaneous combustion and defect introduction, although a small amount of surface oxidation is generated on the interlayer Cu or Ni, the upper and lower nano-porous active layers are still metallurgically combined with the Cu or Ni, and the Cu or Ni is used as a supporting layer and acts as a current collector, so that the brittleness problem of a nano-porous structure is effectively inhibited, and the conductivity is improved;
(4) defects including metal vacancies, oxygen vacancies and the like can be obviously introduced into the oxide layer by annealing treatment in a hydrogen atmosphere, and metal elements generated in the reduction process are doped in crystal lattices in an atomic scale, so that the arrangement of a surrounding electric field is improved; the occurrence of oxygen vacancies not only improves the conductivity, but also creates more active sites and provides more active sites for the oxidation-reduction reaction;
(5) at a current density of 0.5mA cm-2The specific area capacity can be more than 9.48mAh cm-2Simultaneous cycle and rate performance improvementHigh.
Drawings
FIG. 1 is a flow chart of the preparation method of the flexible nano-porous metal oxide negative electrode for the secondary battery according to the invention;
FIG. 2 (a) is a digital photograph of a batch prepared electrode sample after spontaneous combustion treatment; (b) digital photographic images of electrode samples prepared in batches for reduction processing;
FIG. 3 (a) is a microscopic SEM topography after dealloying, auto-ignition and reduction treatments of NiCoMn/Cu/NiCoMn; (b) is a microscopic SEM appearance picture of NiCuMn/Cu/NiCuMn after dealloying, spontaneous combustion and reduction treatment.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
A preparation method of a flexible nano porous metal oxide negative electrode for a lithium ion battery comprises the following steps:
(1) preparing the alloy foil strip: polishing and grinding two NiCuMn alloys or two NiCoMn alloys with the thickness of 1cm, cleaning with alcohol, drying, then selecting Cu or Ni plates with the thickness of 1-2mm as an intermediate interlayer for symmetrical edge sealing and vacuum sheath welding, heating the wrapped and welded laminated plate to 600-1000 ℃, carrying out hot rolling after carrying out heat preservation for 30-120min, controlling the rolling amount to be within 30%, carrying out repeated rolling to obtain a plate with the thickness of 1mm, and carrying out repeated vacuum annealing and cold rolling on the plate to obtain an alloy foil belt with the thickness of 50-200 um;
(2) preparing flexible nano-porous alloy oxide: placing the alloy foil tape in 1mol/L ammonium sulfate, dealloying in a water bath at 60 ℃ to prepare a nano porous alloy, cleaning the nano porous alloy, directly taking out the cleaned nano porous alloy from absolute ethyl alcohol, placing the cleaned nano porous alloy in a ventilation position, and performing self-propagating combustion to generate a flexible nano porous alloy oxide electrode;
(3) preparing a defect nano porous alloy oxide electrode: and (3) placing the flexible nano-porous alloy oxide foil strip in a hydrogen furnace for annealing treatment to prepare the flexible nano-porous alloy oxide electrodes with different defect degrees and metal doping.
Further, in the step (1), in the NiCuMn alloy, the molar mass fraction of Mn is 60-70%, the molar mass fraction of Ni is 5-25%, and the balance is the molar mass fraction of Cu; the molar mass of Mn in the NiCoMn alloy is 60-70%, the molar mass of Ni is 5-25%, and the balance is the molar mass of Co.
The alloy foil strip prepared in the step (1) is a NiCuMn/Cu/NiCuMn alloy foil strip, a NiCoMn/Cu/NiCoMn alloy foil strip, a NiCuMn/Ni/NiCuMn alloy foil strip or a NiCoMn/Ni/NiCoMn alloy foil strip.
The temperature of the vacuum annealing in the step (1) is 600-800 ℃.
The nano-porous alloy prepared in the step (2) is NiCuMn/Cu/NiCuMn nano-porous alloy, NiCoMn/Cu/NiCoMn nano-porous alloy, NiCuMn/Ni/NiCuMn nano-porous alloy or NiCoMn/Ni/NiCoMn nano-porous alloy.
In the step (3), the annealing temperature is controlled to be 200-900 ℃, and the annealing time is controlled to be 5-180 min.
The nano porous metal is subjected to self-propagating combustion in the air atmosphere to prepare the low-energy-consumption oxide.
The flexible nano porous metal oxide cathode prepared by the preparation method is applied to secondary batteries, and the secondary batteries comprise lithium ion batteries, sodium ion batteries and potassium ion batteries.
Example 1
An alloy foil with the thickness of 100um, which is prepared by rolling Ni20Cu10Mn70 (molar ratio) alloy and sandwich metal Ni according to the thickness ratios of 5: 1: 5, 8: 1: 8 and 10: 1: 10 respectively, is corroded in ammonium sulfate of 1mol/L to prepare the flexible nano-porous alloy foil. Direct packaging test analysis after spontaneous combustion in air found that the current density was 0.5A cm-2The specific area capacity is 5.1, 6.2 and 7.7mAh cm-2. After the circulation is performed for 100 circles at the same time, the capacity is respectively kept at 1.3, 1.8 and 2.5mAh cm-2;
The alloy foil with the thickness of 100um prepared by rolling the alloy Ni20Cu10Mn70 and the sandwich metal Cu according to the thickness ratio of 5: 1: 5, 8: 1: 8 and 10: 1: 10 respectively is corroded in 1mol/L ammonium sulfate to prepare the flexible nano porous alloy foil. Direct packaging test analysis after spontaneous combustion in air found that the current density was 0.5A cm-2The specific area capacity is 5.4, 6.4 and 7.8mAh cm-2. After the circulation is performed for 100 circles at the same time, the capacity is respectively kept at 1.6, 1.95 and 2.8mAh cm-2。
Example 2
The alloy foil with the thickness of 100um prepared by rolling the alloy Ni20Co10Mn70 and the sandwich metal Ni according to the thickness ratio of 5: 1: 5, 8: 1: 8 and 10: 1: 10 respectively is corroded in 1mol/L ammonium sulfate to prepare the flexible nano porous alloy foil. Direct packaging test analysis after spontaneous combustion in air found that the current density was 0.5A cm-2The specific area capacity is respectively 6.2, 7.6 and 9.2mAh cm-2. After the circulation is performed for 100 circles at the same time, the capacity is respectively kept at 2.1, 3.2 and 3.8mAh cm-2;
The alloy foil with the thickness of 100um prepared by rolling the alloy Ni20Co10Mn70 and the sandwich metal Cu according to the thickness ratio of 5: 1: 5, 8: 1: 8 and 10: 1: 10 respectively is corroded in 1mol/L ammonium sulfate to prepare the flexible nano porous alloy foil. Direct packaging test analysis after spontaneous combustion in air found that the current density was 0.5A cm-2The specific area capacities thereof were 6.6, 7.9 and 9.3mAh cm-2. After the circulation is performed for 100 circles at the same time, the capacity is respectively kept at 2.4, 3.3 and 3.9mAh cm-2。
Example 3
Preferably Ni20Cu10Mn70 is used as a master alloy interlayer metal, preferably Cu, and the prepared 100um thick nano porous foil is subjected to spontaneous combustion, and is subjected to reduction treatment at 200 ℃ for 10min to prepare an electrode with the current density of 0.5A cm-2The specific area capacity is 5-10mAh cm-2After 100 cycles of the cycle, the capacity is still kept between 4 and 8mAh cm-2To (c) to (d);
preferably Ni20Cu10Mn70 is used as a master alloy interlayer metal, preferably Cu, and the prepared 100um thick nano porous foil is subjected to spontaneous combustion, and is subjected to reduction treatment at 200 ℃ for 120min to prepare an electrode with the current density of 0.5A cm-2The specific area capacity is 4-9mAh cm-2After 100 cycles of the cycle, the capacity is still maintained at 3-7mAh cm-2In the meantime.
Example 4
Preferably Ni20Co10Mn70 is used as a master alloy interlayer metal, preferably Cu, and the prepared 100um thick nano porous foil is subjected to spontaneous combustion, and then is subjected to reduction treatment at 600 ℃ for 60min to prepare an electrode with the current density of 0.5A cm-2The specific area capacity is 2-7mAh cm-2After 100 cycles of the cycle, the capacity is still kept between 0.2 and 4mAh cm-2To (c) to (d);
preferably Ni20Co10Mn70 is used as a master alloy interlayer metal, preferably Cu, and the prepared 100um thick nano porous foil is subjected to spontaneous combustion, and is subjected to reduction treatment at 600 ℃ for 120min to prepare an electrode with the current density of 0.5A cm-2The specific area capacity is 1-6.5mAh cm-2After 100 cycles of the cycle, the capacity is still kept between 0.1 and 3.3mAh cm-2In the meantime.
According to the flexible nano porous metal oxide cathode for the secondary battery and the preparation method thereof, disclosed by the invention, the nano porous metal is introduced into the batch preparation of the cathode material for the lithium ion battery by self-propagating combustion for the first time, the preparation process is simple, and the cost is low; spontaneous combustion can cause rapid oxidation of the surface and coarsening of the pore structure, resulting in a highly active material loaded nanoporous integrated electrode (> 7mg cm)-2) (ii) a In the annealing treatment of dealloying, spontaneous combustion and defect introduction, although a small amount of surface oxidation is generated on the interlayer Cu or Ni, the upper and lower nano-porous active layers are still metallurgically combined with the Cu or Ni, and the Cu or Ni is used as a supporting layer and acts as a current collector, so that the brittleness problem of a nano-porous structure is effectively inhibited, and the conductivity is improved; defects including metal vacancies, oxygen vacancies and the like can be obviously introduced into the oxide layer by annealing treatment in a hydrogen atmosphere, and metal elements generated in the reduction process are doped in crystal lattices in an atomic scale, so that the arrangement of a surrounding electric field is improved; oxygen gasThe occurrence of the vacancy not only improves the conductivity, but also creates more active sites and provides more active sites for the oxidation-reduction reaction; at a current density of 0.5mA cm-2The specific area capacity can be more than 9.48mAh cm-2And meanwhile, the cycle and rate performance are obviously improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a flexible nano porous metal oxide cathode for a secondary battery is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing the alloy foil strip: polishing and grinding two NiCuMn alloys or two NiCoMn alloys with the thickness of 1cm, cleaning with alcohol, drying, then selecting Cu or Ni plates with the thickness of 1-2mm as an intermediate interlayer for symmetrical edge sealing and vacuum sheath welding, heating the wrapped and welded laminated plate to 600-1000 ℃, carrying out hot rolling after carrying out heat preservation for 30-120min, controlling the rolling amount to be within 30%, carrying out repeated rolling to obtain a plate with the thickness of 1mm, and carrying out repeated vacuum annealing and cold rolling on the plate to obtain an alloy foil belt with the thickness of 50-200 um;
(2) preparing flexible nano-porous alloy oxide: placing the alloy foil tape in 1mol/L ammonium sulfate, dealloying in a water bath at 60 ℃ to prepare a nano porous alloy, cleaning the nano porous alloy, directly taking out the cleaned nano porous alloy from absolute ethyl alcohol, placing the cleaned nano porous alloy in a ventilation position, and performing self-propagating combustion to generate a flexible nano porous alloy oxide electrode;
(3) preparing a defect nano porous alloy oxide electrode: and (3) placing the flexible nano-porous alloy oxide foil strip in a hydrogen furnace for annealing treatment to prepare the flexible nano-porous alloy oxide electrodes with different defect degrees and metal doping.
2. The method of claim 1, wherein the method comprises the steps of: in the step (1), in the NiCuMn alloy, the molar mass fraction of Mn is 60-70%, the molar mass fraction of Ni is 5-25%, and the balance is the molar mass fraction of Cu; the molar mass of Mn in the NiCoMn alloy is 60-70%, the molar mass of Ni is 5-25%, and the balance is the molar mass of Co.
3. The method of claim 1, wherein the method comprises the steps of: the alloy foil strip prepared in the step (1) is a NiCuMn/Cu/NiCuMn alloy foil strip, a NiCoMn/Cu/NiCoMn alloy foil strip, a NiCuMn/Ni/NiCuMn alloy foil strip or a NiCoMn/Ni/NiCoMn alloy foil strip.
4. The flexible nanoporous metal oxide anode for secondary batteries and the method for preparing the same as claimed in claim 1, wherein: the temperature of the vacuum annealing in the step (1) is 600-800 ℃.
5. The flexible nanoporous metal oxide anode for secondary batteries and the method for preparing the same as claimed in claim 1, wherein: the nano-porous alloy prepared in the step (2) is NiCuMn/Cu/NiCuMn nano-porous alloy, NiCoMn/Cu/NiCoMn nano-porous alloy, NiCuMn/Ni/NiCuMn nano-porous alloy or NiCoMn/Ni/NiCoMn nano-porous alloy.
6. The flexible nanoporous metal oxide anode for secondary batteries and the method for preparing the same as claimed in claim 1, wherein: in the step (3), the annealing temperature is controlled to be 200-900 ℃, and the annealing time is controlled to be 5-180 min.
7. The flexible nanoporous metal oxide anode for secondary batteries and the method for preparing the same as claimed in claim 1, wherein: the nano porous metal is subjected to self-propagating combustion in the air atmosphere to prepare the low-energy-consumption oxide.
8. The flexible nano-porous metal oxide anode prepared by the preparation method according to any one of claims 1 to 7 is applied to secondary batteries, wherein the secondary batteries comprise lithium ion batteries, sodium ion batteries and potassium ion batteries.
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CN113258050A (en) * | 2020-12-23 | 2021-08-13 | 天津工业大学 | Five-element high-entropy alloy oxide negative electrode material and preparation method and application thereof |
CN114023928A (en) * | 2021-08-31 | 2022-02-08 | 天津大学 | Preparation method for in-situ construction of bimetallic oxide integrated electrode by hierarchical porous copper |
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