CN103367756B - Preparation method of porous copper based lithium ion battery anode material - Google Patents

Preparation method of porous copper based lithium ion battery anode material Download PDF

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CN103367756B
CN103367756B CN201310309769.7A CN201310309769A CN103367756B CN 103367756 B CN103367756 B CN 103367756B CN 201310309769 A CN201310309769 A CN 201310309769A CN 103367756 B CN103367756 B CN 103367756B
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copper foil
electrolyte
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CN103367756A (en
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司鹏超
李辉
范丽娟
肖鑫鑫
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Shandong University
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Abstract

The invention relates to a preparation method of a porous copper based lithium ion battery anode material. The preparation method comprises the following steps: using a mixed solution of KOH and NH4Cl as a constant potential oxidation electrolyte to carry out in situ oxidation reduction on copper foil so as to prepare porous copper, depositing molybdenum disulfide on the porous copper by cyclic voltammetry or potentiostatic method by using a mixed solution of (NH4)2MoS4 and KCl as an electrolyte, and carrying out heat treatment so as to obtain an MoS2/porous copper composite material. As the composite material, which is prepared by the utilization of cyclic voltammetry for deposition of molybdenum disulfide and has large specific surface area, is used as an anode material of a lithium sulphur battery, initial discharging reaches 1900 mAh/g, and cycling basically maintains stable. The composite material obtained by the potentiostatic method for deposition of molybdenum disulfide has good cycling stability and basically has no attenuation after 100 times of cycling.

Description

A kind of preparation method of the lithium ion battery negative material based on Porous Cu
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, belong to the field such as new forms of energy, new material.
Background technology
Copper is a kind of good current collector material, and the copper of loose structure possesses the ability of larger specific surface and stronger accommodation active material, greatly can improve the capacity of lithium ion battery.Patent CN102683656A discloses a kind of high performance lithium ion battery three dimensional apertured film silicon based anode material and preparation method thereof, adopts and has three-dimensional porous current collector material, as Copper Foil net, copper mesh, foam copper or nickel foam; In Copper Foil net, copper mesh, foam copper or nickel foam, form one deck silicon thin film or silicon-metal laminated film with magnetically controlled sputter method, then form three dimensional apertured film silicon based anode material by heat treatment mode.
Sulphur has theoretical specific capacity high (1675mAh/g), theoretical voltage high (2.287V), the advantages such as theoretical energy density high (3824Wh/kg), it and lithium metal form the theoretical specific energy of lithium-sulfur cell can up to 2600Wh/kg, simultaneously sulphur also has aboundresources, the feature such as cheap, environmentally friendly, so it is a kind of negative material having the high-energy-density of application prospect.Nowadays graphite is used as the standard negative material of lithium ion battery, but be only 372mAh/g and there is safety problem due to its theoretical specific capacity, therefore the application in high-performance lithium ion battery is restricted.The theoretical specific energy of lithium-sulfur cell can up to 2600Wh/kg.Inst. of Physics, CAS utilizes mesoporous molecular sieve SBA-15 as template, with phosphomolybdic acid (H 3pMo 12o 40) for precursor power goes out to have the mesoporous molybdenum bisuphide of two-dimentional six side's substructures, first discharge specific capacity is about 880mAh/g, obtains the reversible specific capacity of 630mAh/g after 20 circulations.Feng of Hubei University etc. utilize thio urea (CS (NH 2) 2), Ammonium Molybdate Tetrahydrate ((NH 4) 6mo 7o 244H 2and oxalic acid (H O) 2c 2o 42H 2o) MoS of obtained nano-sheet 2, it can be used as active material under discharge current density is the condition of 60mA/g, first discharge specific capacity is 1174.7mAh/g, and cyclical stability is good, still keeps the reversible specific capacity of 851.5mAh/g after 20 circulations.By molybdenum bisuphide and material with carbon element or conducting polymer compound to improve its performance, but prepare in electrode process and usually need adhesive, the utilance of electrode is declined and complicated process of preparation.
How copper, sulphur are combined in the effect playing battery in electrode better, significant.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the lithium ion battery negative material based on Porous Cu, to improve specific capacity and the charge and discharge cycles ability of negative material.
The technical scheme that the present invention takes is:
Based on a preparation method for the lithium ion battery negative material of Porous Cu, comprise step as follows:
(1) Porous Cu is prepared in in-situ oxidation reduction: with KOH and NH 4cl mixed solution is constant potential oxidation electrolyte, with pretreated Copper Foil of polishing for work electrode, is to electrode and reference electrode with platinum, at 5 ~ 8V voltage, and oxidation 300 ± 50s; Then using the Copper Foil after above-mentioned oxidation as work electrode, platinized platinum is done electrode, and saturated calomel electrode makes reference electrode, and NaOH solution makes electrolyte, and the negative potential applying-1.2V carries out in-situ reducing 300 ± 50s to the oxide of copper foil surface, obtained Porous Cu;
(2) electrochemical reduction deposition molybdenum bisuphide on Porous Cu: take Porous Cu as work electrode, platinized platinum is done electrode, and saturated calomel electrode makes reference electrode, with (NH 4) 2moS 4be electrolyte with KCl mixed solution, cyclic voltammetry or potentiostatic method deposition molybdenum bisuphide, voltage range during cyclic voltammetry deposition is 0.2 ~-1.3V, and sweep speed is 0.05V/s, deposition 10 ~ 20 circle; During potentiostatic method deposition, current potential is that-1.2V arrives-1.1, and sedimentation time is 60 ± 5s;
(3) heat-treat at the Copper Foil of 450 ± 20 DEG C of temperature to deposition molybdenum bisuphide, heat treatment time is 1h, uses N in heat treatment process 2gas is protected sample, obtains product MoS 2/ Porous Cu composite material.
In said method, KOH and NH described in step (1) 4two solute concentrations of Cl mixed solution are respectively 0.15mol/L and 0.1mol/L; Described copper thickness is 50 ± 10 μm, and the concentration of NaOH solution is 0.1mol/L.
(NH described in step (2) 4) 2moS 40.005mol/L and 0.1mol/L is respectively with KCl mixed solution two solute concentration.
Assembled battery: electrolyte is electrolyte for lithium ion battery, MoS 2/ Porous Cu composite material is as pole piece, and lithium sheet is as to pole.
The invention has the beneficial effects as follows:
But the less satisfactory mechanical property of Copper Foil specific area growth that in-situ oxidation reducing process is obtained.Utilize cyclic voltammetry the to deposit composite material of bigger serface that molybdenum bisuphide obtains discharges first as the negative material of lithium-sulfur cell and reaches 1900mAh/g, circulation kept stable; The composite material stable circulation performance utilizing potentiostatic method deposition molybdenum bisuphide to obtain is fine, substantially undamped after 100 circulations.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of pure copper foil and the Copper Foil after in-situ oxidation reduces, and 1 is pure copper foil, and 2,3 is the Copper Foil after in-situ oxidation reduction;
The dull and stereotyped copper of Fig. 2 and the CV(cyclic voltammetry of Porous Cu in 0.1M NaOH solution) comparison diagram;
Fig. 3 is that the Copper substrate SEM that cyclic voltammetry and potentiostatic method deposit after molybdenum bisuphide schemes, and a, b are cyclic voltammetry, and c, d are potentiostatic method;
MoS prepared by Fig. 4 cyclic voltammetry 2/ Porous Cu composite material specific capacity is with the variation tendency of cycle-index;
MoS prepared by Fig. 5 potentiostatic method 2the specific capacity of/Porous Cu composite material is with the variation tendency of cycle-index.
Embodiment
Further illustrate below in conjunction with embodiment.
Embodiment 1
Based on a preparation method for the lithium ion battery negative material of Porous Cu, comprise step as follows:
(1), Porous Cu is prepared
Preliminary treatment: be the small pieces that the Copper Foil of 50um cuts as 10mm × 20mm size by thickness, use #180, #320, #600, #800 liquid honing successively, then with the polishing of #600, #1000 abrasive paper for metallograph, while removing surface oxides, make its surface as far as possible smooth.The Copper Foil of having polished is cleaned to remove the organic substance on its surface and residual oxide skin with the sulfuric acid solution of acetone, 0.05M successively, finally falls the residual sulfuric acid of copper foil surface by washed with de-ionized water.
In-situ oxidation: utilize constant potential technology to be oxidized by copper foil surface on LK2005A type electrochemical workstation, utilizes 0.15M KOH+0.1M NH 4the mixed solution of Cl makes electrolyte, and work electrode made by Copper Foil, and platinized platinum is done electrode and reference electrode, and constant potential 6V keeps 300s.Be oxidized complete washed with de-ionized water Copper Foil to remove the electrolyte of its remained on surface.
In-situ reducing: the Copper Foil after above-mentioned oxidation is as work electrode, and platinized platinum is done electrode, and saturated calomel electrode makes reference electrode, and 0.1M NaOH solution makes electrolyte, and the negative potential applying-1.2V carries out in-situ reducing to the oxide of copper foil surface.
(2), molybdenum bisuphide is deposited
Using the Copper Foil of above-mentioned process as matrix, cathode reduction method is utilized to deposit molybdenum bisuphide thereon: to utilize 0.005M (NH 4) 2moS 4the mixed solution of+0.1M KCl is as electrolyte, Copper substrate makes work electrode, and platinized platinum is done electrode, and saturated calomel electrode makes reference electrode, utilize cyclic voltammetry, make tetrathio molybdenum acid ion obtain electronics on the working electrode (s and be reduced to molybdenum bisuphide and be deposited on copper foil surface.Voltage range wherein during cyclic voltammetry deposition selects 0.2 ~-1.3V, and sweep speed is set to 0.05V/s, deposition 10 circle.React rear washed with de-ionized water Copper Foil, and vacuumize at normal temperatures.
At 450 DEG C of temperature, the Copper Foil of deposition molybdenum bisuphide is heat-treated, in heat treatment process, use N 2gas is protected sample, at high temperature reacts with oxygen to prevent molybdenum bisuphide.
(3) assembled battery
By above-mentioned obtained MoS 2/ Porous Cu composite material is as pole piece, lithium sheet is as to pole, using the electrolyte for lithium ion battery (product type is for LBC305-01) of Shenzhen Xinzhoubang Technology Co., Ltd's production as electrolyte, using polypropylene film as barrier film, half-cell is assembled in glove box (that (China) Co., Ltd of meter Kai Luo, Super1220/750).Assembled battery process is as follows:
Lower casing → a drip 1-2 drips electrolyte pole piece → a drip 1-2 and drips electrolyte → lithium sheet and (should be noted herein and use plastic tweezer to place lithium sheet, and avoid lithium sheet to contact with lower casing, in order to avoid pole piece and the direct or indirect UNICOM of lithium sheet and short circuit) → 1-2 sheet nickel foam (sheet of use is several to be determined according to the thickness of pole piece) → a drip 8-10 drips electrolyte (observing nickel foam all to soak) → buckle well upper casing (also needing with plastic tweezer in order to avoid short circuit) → seal herein.
Embodiment 2
Based on a preparation method for the lithium ion battery negative material of Porous Cu, comprise step as follows:
(1) Porous Cu is prepared
Preliminary treatment: be the small pieces that the Copper Foil of 50um cuts as 10mm × 20mm size by thickness, use #180, #320, #600, #800 liquid honing successively, then with the polishing of #600, #1000 abrasive paper for metallograph, while removing surface oxides, make its surface as far as possible smooth.The Copper Foil of having polished is cleaned to remove the organic substance on its surface and residual oxide skin with the sulfuric acid solution of acetone, 0.05M successively, finally falls the residual sulfuric acid of copper foil surface by washed with de-ionized water.
In-situ oxidation: utilize constant potential technology to be oxidized by copper foil surface on LK2005A type electrochemical workstation, utilizes 0.15M KOH+0.1M NH 4the mixed solution of Cl makes electrolyte, and work electrode made by Copper Foil, and platinized platinum is done electrode and reference electrode, and constant potential 5V keeps 350s.Be oxidized complete washed with de-ionized water Copper Foil to remove the electrolyte of its remained on surface.
In-situ reducing: the Copper Foil after above-mentioned oxidation is as work electrode, and platinized platinum is done electrode, and saturated calomel electrode makes reference electrode, and 0.1M NaOH solution makes electrolyte, and the negative potential applying-1.2V carries out in-situ reducing to the oxide of copper foil surface.
(2) molybdenum bisuphide is deposited
Using the Copper Foil of above-mentioned process as matrix, cathode reduction method is utilized to deposit molybdenum bisuphide thereon: to utilize 0.005M (NH 4) 2moS 4the mixed solution of+0.1M KCl is as electrolyte, Copper substrate makes work electrode, and platinized platinum is done electrode, and saturated calomel electrode makes reference electrode, utilize potentiostatic method, make tetrathio molybdenum acid ion obtain electronics on the working electrode (s and be reduced to molybdenum bisuphide and be deposited on copper foil surface.During potentiostatic method deposition, current potential is-1.2V, and sedimentation time is 60s; React rear washed with de-ionized water Copper Foil, and vacuumize at normal temperatures.
At 450 DEG C of temperature, the Copper Foil of deposition molybdenum bisuphide is heat-treated, in heat treatment process, use N 2gas is protected sample, at high temperature reacts with oxygen to prevent molybdenum bisuphide.
(3) assembled battery
By above-mentioned obtained MoS 2/ Porous Cu composite material is as pole piece, lithium sheet is as to pole, using the electrolyte for lithium ion battery (product type is for LBC305-01) of Shenzhen Xinzhoubang Technology Co., Ltd's production as electrolyte, using polypropylene film as barrier film, half-cell is assembled in glove box (that (China) Co., Ltd of meter Kai Luo, Super1220/750).Assembled battery process is as follows:
Lower casing → a drip 1-2 drips electrolyte pole piece → a drip 1-2 and drips electrolyte → lithium sheet and (should be noted herein and use plastic tweezer to place lithium sheet, and avoid lithium sheet to contact with lower casing, in order to avoid pole piece and the direct or indirect UNICOM of lithium sheet and short circuit) → 1-2 sheet nickel foam (sheet of use is several to be determined according to the thickness of pole piece) → a drip 8-10 drips electrolyte (observing nickel foam all to soak) → buckle well upper casing (also needing with plastic tweezer in order to avoid short circuit) → seal herein.
Performance test
Adopt the means such as SEM to carry out Microstructure characterization, utilize electrochemical workstation and battery test system to study its electrochemical behavior and battery electrode performance simultaneously.
In course of reaction, the appearance at redox peak is the gain and loss owing to there is electronics as shown in Figure 2, and peak value size and current value are determined by the number of electrons passed through, also namely the large I reflection of peak value participates in the amount of the Cu of reaction, in addition the larger Cu participating in reacting of surface area is just more, thus can so as to characterizing the long-pending size of copper foil surface.
The sample that in Fig. 3, cyclic voltammetry deposition molybdenum bisuphide obtains has lost the pattern of Copper substrate substantially, but the sample that potentiostatic method obtains still keeps the pattern of Copper substrate.
Find out in Fig. 4, Fig. 5 that utilize cyclic voltammetry the to deposit composite material of bigger serface that molybdenum bisuphide obtains discharges first as the negative material of lithium-sulfur cell and reach 1900mAh/g, but stable circulation is unsatisfactory, in 20 circulations, special capacity fade is 200mAh/g, but kept stable afterwards; Although the composite material specific capacity utilizing potentiostatic method deposition molybdenum bisuphide to obtain only has 550mAh/g, stable circulation performance is fine, substantially undamped after 100 circulations.

Claims (3)

1. based on a preparation method for the lithium ion battery negative material of Porous Cu, it is characterized in that, comprise step as follows:
(1) Porous Cu is prepared in in-situ oxidation reduction: with KOH and NH 4cl mixed solution is constant potential oxidation electrolyte, with pretreated Copper Foil of polishing for work electrode, is to electrode and reference electrode with platinum, at 5 ~ 8V voltage, and oxidation 300 ± 50s; Then using the Copper Foil after above-mentioned oxidation as work electrode, platinized platinum is done electrode, and saturated calomel electrode makes reference electrode, and NaOH solution makes electrolyte, and the negative potential applying-1.2V carries out in-situ reducing 300 ± 50s to the oxide of copper foil surface, obtained Porous Cu;
(2) electrochemical reduction deposition molybdenum bisuphide on Porous Cu: take Porous Cu as work electrode, platinized platinum is done electrode, and saturated calomel electrode makes reference electrode, with (NH 4) 2moS 4be electrolyte with KCl mixed solution, cyclic voltammetry or potentiostatic method deposition molybdenum bisuphide, voltage range during cyclic voltammetry deposition is 0.2 ~-1.3V, and sweep speed is 0.05V/s, deposition 10 ~ 20 circle; During potentiostatic method deposition, current potential is-1.2V to-1.1V, and sedimentation time is 60 ± 5s;
(3) heat-treat at the Copper Foil of 450 ± 20 DEG C of temperature to deposition molybdenum bisuphide, heat treatment time is 1h, uses N in heat treatment process 2gas is protected sample, obtains product MoS 2/ Porous Cu composite material.
2. the preparation method of a kind of lithium ion battery negative material based on Porous Cu according to claim 1, is characterized in that, KOH and NH described in step (1) 4the solute concentration of Cl mixed solution is respectively 0.15mol/L and 0.1mol/L, and the concentration of NaOH solution is 0.1mol/L.
3. the preparation method of a kind of lithium ion battery negative material based on Porous Cu according to claim 1, is characterized in that, (NH in the electrolyte described in step (2) 4) 2moS 40.005mol/L and 0.1mol/L is respectively with the concentration of KCl.
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CN103602972B (en) * 2013-11-28 2015-11-04 长春吉大科诺科技有限责任公司 A kind of surface treatment method of negative current collector copper foil of lithium ion battery
CN104614433A (en) * 2015-02-13 2015-05-13 天津力神电池股份有限公司 Evaluation method for gram volume of graphite cathode material
CN106884190A (en) * 2015-12-15 2017-06-23 中国科学院大连化学物理研究所 A kind of preparation of classifying porous material and classifying porous material
CN105442012B (en) * 2016-01-07 2018-06-01 河南工程学院 A kind of composite nano materials MoS2/TiO2The preparation method and applications of nano-tube array
CN106654259A (en) * 2016-07-27 2017-05-10 北京航空航天大学 Preparation method for molybdenum disulfide nanosheet lithium ion battery negative electrode material by physical method
CN110380056B (en) * 2019-07-18 2021-02-02 中国科学院宁波材料技术与工程研究所 Surface modified current collector, and preparation method and application thereof
CN111029589A (en) * 2019-12-23 2020-04-17 昆明理工大学 Preparation method and application of composite lithium metal negative electrode material
CN112467141A (en) * 2020-11-12 2021-03-09 黑龙江工业学院 Preparation method of high-rate lithium ion battery negative electrode active material
CN114023964B (en) * 2021-10-27 2023-03-28 武汉理工大学 Composite zinc foil with zinc oxide particle protective layer and preparation method and application thereof

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