CN103887485A - Doped nanometer vanadium pentoxide membrane electrode material for lithium ion battery - Google Patents

Doped nanometer vanadium pentoxide membrane electrode material for lithium ion battery Download PDF

Info

Publication number
CN103887485A
CN103887485A CN201410108180.5A CN201410108180A CN103887485A CN 103887485 A CN103887485 A CN 103887485A CN 201410108180 A CN201410108180 A CN 201410108180A CN 103887485 A CN103887485 A CN 103887485A
Authority
CN
China
Prior art keywords
oxide
electrode material
lithium ion
ion battery
membrane electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410108180.5A
Other languages
Chinese (zh)
Inventor
余丹梅
谯亚娟
李抄
周晓媛
陈昌国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chongqing University
Original Assignee
Chongqing University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chongqing University filed Critical Chongqing University
Priority to CN201410108180.5A priority Critical patent/CN103887485A/en
Publication of CN103887485A publication Critical patent/CN103887485A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • 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
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a doped nanometer vanadium pentoxide membrane electrode material for a lithium ion battery, the electrode material comprises Co-V oxide, Mn-V oxide, Ni-V oxide or the random combination of the oxides, wherein Co, Mn, and Ni elements of the Co-V oxide, the Mn-V oxide and the Ni-V oxide comes from one or the mixture of at least two out of respective oxide, hydroxide or salt; the electrode material is obtained through preparing a doped V205 sol and the doped nanometer V205 membrane electrode. The doped nanometer vanadium pentoxide membrane electrode material for the lithium ion battery provided by the invention is characteristics that the electrode material has high specific capacity, good cycle performance and large-ratio charge and discharge performance, so that the problem of low specific capacity of a lithium ion battery is solved effectively, and the preparation method is simple and convenient and low in cost, and obviously improves the application value of the V205 as the anode material of a lithium ion battery.

Description

Dopen Nano vanadic oxide thin-film electrode material for a kind of lithium ion battery
Technical field
The present invention relates to nano material and lithium ion battery technologic material field, be specifically related to a kind of lithium ion battery dopen Nano vanadic oxide (V 2o 5) thin-film electrode material.
Background technology
Lithium ion battery is a kind of new electric energy storage facilities growing up last century, has the features such as voltage is high, specific capacity large, have extended cycle life.In recent years, along with popularizing fast that lithium ion battery uses in fields such as war industry, space technology, engineering in medicine, electric automobile, microelectronics industry, people have proposed more and more higher requirement to performance of lithium ion battery.Lithium ion battery is made up of parts such as positive and negative pole material, electrolyte, barrier films, and wherein the quality of positive electrode performance is the key that determines battery performance.
At present, for the positive electrode of lithium ion battery, be mainly the LiMO with layer structure 2, olivine structural LiMPO 4(wherein: the transition metals such as M=Ni, Co, Mn, Fe), spinel-type LiMn 2o 4, and various multicomponent system.And realize business-like stratiform LiCoO 2although it is high to have operating voltage, charging/discharging voltage is steady, the advantages such as good cycle, but cobalt resource scarcity, expensive, utilance is low, specific capacity is not high, and its actual specific capacity is only 50% left and right of theoretical capacity (274mAh/g), simultaneously when synthetic material, adopt the complex process such as high temperature solid-state is synthetic, method that energy consumption is high more.Olivine structural LiFePO 4have Heat stability is good, security performance advantages of higher, but exist the problems such as the irreversible capacity height causing because of low conductivity, and theoretical specific capacity is only 170mAh/g, actual specific capacity only has 140mAh/g.Although spinel-type LiMn 2o 4have easily synthetic, the advantage such as security performance is good, have John-Teller effect but take off in process in lithium ion embedding, molecular geometry distorts, and has reduced the symmetry of spinel structure, causes cycle performance variation.The specific capacity of above-mentioned material and cycle performance are all lower.
Due to special layer structure, V 2o 5have larger specific capacity (theoretical capacity is 442mAh/g).But in battery charge and discharge process, V 2o 5still there is the defects such as structural instability, electronic conductivity and ionic conductivity are low, cause the problems such as charge-discharge performance is poor, specific capacity is low, energy density is low to produce.At present, improve V 2o 5the method of performance mainly contains two aspects: the one, prepare nano material by changing synthetic method, and increase specific area, increase interlamellar spacing simultaneously, shorten lithium ion the evolving path, improve the specific capacity of electrode material; The 2nd, improve conductivity by doped metallic elements.That in document, reports at present, improves V 2o 5the method of performance, all exists length consuming time, energy consumption is high, and the shortcoming that need to carry out under the harsh conditions such as high temperature, high pressure, vacuum, as EFI bundle method, ion sputtering method, electrodeposition process, chemical vapour deposition (CVD) etc.And the present invention can a step prepare dopen Nano V 2o 5membrane electrode, does not need to add alite paste and conductive agent, and technique is simple, and time consumption and energy consumption are low, have and easily realize industrialized potentiality.
Summary of the invention
The object of the present invention is to provide a kind of energy consumption low, time consume low, technique is simple, the lithium ion battery of with low cost, function admirable dopen Nano vanadic oxide thin-film electrode material.
Dopen Nano vanadic oxide thin-film electrode material for lithium ion battery involved in the present invention, comprise the combination in any of Co-V oxide, Mn-V oxide, Ni-V oxide or above-mentioned oxide, Co, Mn in described Co-V oxide, Mn-V oxide, Ni-V oxide, Ni element derive from the mixture of a kind of in oxide, hydroxide and salt separately or at least two kinds, dopen Nano vanadic oxide thin-film electrode material is that length is 500～600nm, wide is 150～200nm, and thick is the cuboid nanometer sheet of 60～90nm;
Lithium ion battery involved in the present invention obtains by following preparation method with dopen Nano vanadic oxide thin-film electrode material:
(1) doping V 2o 5the preparation of colloidal sol: first take V 2o 5powder and Co, Mn, Ni element come the mixture of a kind of of source compound or at least two kinds, wherein m (Co): m (V 2o 5) be 2.0%～2.8%, m (Mn): m (V 2o 5) be 2.0%, m (Ni): m (V 2o 5) be 2.8%, and both are mixed; Then get the hydrogen peroxide (H of 3mL30% 2o 2) solution is placed in the beaker of 25mL, at room temperature, said mixture added wherein, stir, and then add 2mL deionized water to continue to be stirred to form stable rufous vitreosol, be settled to 100mL, obtain the V that adulterates 2o 5colloidal sol;
(2) dopen Nano V 2o 5the preparation of membrane electrode: the Pt sheet deionized water being immersed in hydrogen peroxide is rinsed well, air-dry; Get the above-mentioned doping V of 10 μ L 2o 5colloidal sol, spreads on the Pt sheet of handling well, under room temperature, after natural air drying, is placed in Muffle furnace and calcines 2 hours at 500 ℃, naturally cools to room temperature, obtains dopen Nano V 2o 5membrane electrode, this nano-electrode material is that length is 500～600nm, and wide is 150～200nm, and thick is the cuboid nanometer sheet of 60～90nm.
Co, Mn in described Co-V oxide, Mn-V oxide, Ni-V oxide, Ni element derive from the mixture of a kind of in oxide, hydroxide and salt separately or at least two kinds, and exemplary for example carrys out source compound: cobalt carbonate (CoCO 3), a hydration cobalt carbonate (CoCO 3h 2o), cobaltous sulfate (CoSO 4), Cobalt monosulfate heptahydrate (CoSO 47H 2o), cobalt chloride (CoCl 2), cobalt chloride hexahydrate (CoCl 26H 2o), cobalt nitrate (Co (NO 3) 2), cabaltous nitrate hexahydrate (Co (NO 3) 26H 2o), cobalt oxalate (CoC 2o 4), Diaquaoxalato cobalt (CoC 2o 42H 2o), cobalt acetate (C 2h 3coO 2), cobalt hydroxide (Co (OH) 2), cobalt oxide (CoO), manganese carbonate (MnCO 3), a hydration manganese carbonate (MnCO 3h 2o), manganese sulfate (MnSO 4), four hydrated manganese sulfate (MnSO 44H 2o), manganese chloride (MnCl 2), four hydration manganese chloride (MnCl 24H 2o), manganese nitrate hexahydrate (Mn (NO 3) 26H 2o), manganese oxalate (MnC 2o 4), two oxalic acid hydrate manganese (MnC 2o 42H 2o), manganese acetate (C 4h 6mnO 2), manganous hydroxide (Mn (OH) 2), nickelous carbonate (NiCO 3), six hydration nickel sulfate (NiSO 46H 2o), nickel chloride (NiCl 2), nickel nitrate (NiNO 3), nickel oxalate (C 2h 2o 4ni), nickel acetate tetrahydrate (C 4h 6o 4ni4H 2o), nickel hydroxide (Ni (OH) 2), oxide, hydroxide, salt and the relevant hydrate thereof such as nickel oxide (NiO).
Dopen Nano V involved in the present invention 2o 5thin-film electrode material is that length is 500～600nm, and wide is 150～200nm, and thick is the cuboid nanometer sheet of 60～90nm, as Fig. 1 and Fig. 2, this special pattern has increased the specific area of material widely, has increased the contact area of material and electrolyte, thereby has improved charging and discharging capacity.The nanometer V that is wherein 2.0% containing cobalt amount 2o 5under the condition that membrane electrode is 800mA/g in current density, specific discharge capacity can be up to 729mAh/g, and as Fig. 8, the first five circulation on average decays to weekly 0.94%.The nanometer V that is 2.8% containing cobalt amount 2o 5membrane electrode is in the time that current density is 400mA/g, and specific discharge capacity is 662mAh/g, while increasing current density to 1000mA/g, specific discharge capacity is up to arriving 658mAh/g, while again increasing current density to 8000mA/g, specific discharge capacity is still up to arriving 271mAh/g, as Figure 17.And the stratiform LiCoO of existing market fast sale 2etc. actual specific capacity only～200mAh/g.The nanometer V that is 2.0% containing cobalt amount of the present invention 2o 5membrane electrode has also carried out full battery charging and discharging test, and under the condition that is 687mA/g in current density, specific discharge capacity is up to 710mAh/g, and in 80 discharge cycles tests, on average decay is only 0.60% weekly, as Figure 16.
The manganese nanometer V that mixes of the present invention 2o 5under the condition that membrane electrode is 800mA/g in current density, initial discharge specific capacity can reach 706mAh/g, as Figure 15 d.
The nickel nanometer V that mixes of the present invention 2o 5under the condition that membrane electrode is 800mA/g in current density, initial discharge specific capacity can reach 792mAh/g, as Figure 15 e.
Thereby, with existing lithium ion battery V 2o 5positive electrode is compared, and the present invention has the charge-discharge performance of height ratio capacity, good cycle performance and large multiplying power, illustrate that it not only can effectively solve the problem that lithium ion battery specific capacity is low, and preparation method is easy and simple to handle, with low cost, has significantly improved V 2o 5as the using value of anode material for lithium-ion batteries.
Accompanying drawing explanation
Fig. 1 mixes cobalt nanometer V 2o 5the scanning electron microscope (SEM) photograph (SEM) of thin-film material;
Fig. 2 mixes manganese nanometer V 2o 5the scanning electron microscope (SEM) photograph (SEM) of thin-film material;
Fig. 3 mixes cobalt nanometer V 2o 5the X ray diffracting spectrum (XRD) of thin-film material;
Fig. 4 mixes manganese nanometer V 2o 5the X ray diffracting spectrum (XRD) of thin-film material;
The pure V of Fig. 5 2o 5the cyclic voltammetry curve of membrane electrode, sweep speed is 10mV/s, voltage range is-0.2V～0.6V vs.Ag/AgCl;
The pure V of Fig. 6 2o 5the constant current charge-discharge curve of membrane electrode, current density is 800mA/g, voltage range is-0.1V～0.5V vs.Ag/AgCl;
The nanometer V that Fig. 7 is 2.0% containing cobalt amount 2o 5the cyclic voltammetry curve of membrane electrode, sweep speed is 10mV/s, voltage range is-0.2V～0.6V vs.Ag/AgCl;
The nanometer V that Fig. 8 is 2.0% containing cobalt amount 2o 5the constant current charge-discharge curve of membrane electrode, current density is 800mA/g, voltage range is-0.1V～0.5V vs.Ag/AgCl;
The nanometer V that Fig. 9 is 2.8% containing cobalt amount 2o 5the cyclic voltammetry curve of membrane electrode, sweep speed is 10mV/s, voltage range is-0.2V～0.6V vs.Ag/AgCl;
The nanometer V that Figure 10 is 2.8% containing cobalt amount 2o 5the constant current charge-discharge curve of membrane electrode, current density is 800mA/g, voltage range is-0.1V～0.5V vs.Ag/AgCl;
Figure 11 manganese content is 2.0% nanometer V 2o 5the cyclic voltammetry curve of membrane electrode, sweep speed is 10mV/s, voltage range is-0.2V～0.6V vs.Ag/AgCl;
Figure 12 manganese content is 2.0% nanometer V 2o 5the constant current charge-discharge curve of membrane electrode, current density is 800mA/g, voltage range is-0.1V～0.5V vs.Ag/AgCl;
Figure 13 nickel content is 2.8% nanometer V 2o 5the cyclic voltammetry curve of membrane electrode, sweep speed is 10mV/s, voltage range is-0.1V～0.5V vs.Ag/AgCl;
Figure 14 nickel content is 2.8% nanometer V 2o 5the constant current charge-discharge curve of membrane electrode, current density is 800mA/g, voltage range is-0.1V～0.5V vs.Ag/AgCl;
Figure 15 dopen Nano V 2o 5the discharge capacity attenuation curve of membrane electrode, current density is
800mAh/g, a: pure V 2o 5, b: be 2.0%, c containing cobalt amount: be 2.8%, d containing cobalt amount: manganese content is 2.0%, e: nickel content is 2.0%;
The charge/discharge capacity attenuation curve of Figure 16 lithium ion battery is 2.0% containing cobalt amount;
Under the different current densities of Figure 17, the nanometer V that is 2.8% containing cobalt amount 2o 5the discharge capacity attenuation curve of membrane electrode;
Under the different current densities of Figure 18, the nanometer V that manganese content is 2.0% 2o 5the discharge capacity attenuation curve of membrane electrode.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
Embodiment 1
The related a kind of lithium ion battery of the present embodiment is with mixing cobalt nanometer V 2o 5thin-film electrode material is the product that obtained by the following method, is wherein 2.0% containing cobalt amount:
(1) mix cobalt V 2o 5the preparation of colloidal sol: the 0.146g V first accurately taking 2o 5powder and 0.014g CoSO 47H 2o powder, wherein m (Co): m (V 2o 5) be 2.0%, and both are mixed; Then get the H of 3mL30% 2o 2solution is placed in the beaker of 25mL, at room temperature, the powder of above-mentioned mixing is added wherein, stirs, and then adds 2mL deionized water to continue to be stirred to the stable rufous vitreosol of formation, is settled to 100mL, obtains mixing cobalt V 2o 5colloidal sol.
(2) mix cobalt nanometer V 2o 5the preparation of membrane electrode: the Pt sheet deionized water being immersed in hydrogen peroxide is rinsed well, air-dry; Get the above-mentioned colloidal sol of 10 μ L, spread on the Pt sheet of handling well, under room temperature, after natural air drying, be placed in Muffle furnace and calcine 2 hours at 500 ℃, naturally cool to room temperature, obtain mixing cobalt nanometer V 2o 5membrane electrode.
What the present embodiment was prepared mixes cobalt nanometer V 2o 5the SEM of thin-film material as shown in Figure 1.As can be seen from the figure, V 2o 5film is by evenly and be cuboid nanometer sheet and form, and film has fine and close and feature uniformly.As shown in Figure 3, XRD collection of illustrative plates shows that the thing of product is V mutually 2o 5, 41-1426 is consistent with PDF card, belongs to orthorhombic structure.
What the present embodiment was prepared mixes cobalt nanometer V 2o 5membrane electrode, adopts three-electrode system to test, and three-electrode system is with dopen Nano V 2o 5film is work electrode, and Pt is auxiliary electrode, and Ag/AgCl is reference electrode, the LiClO of 1mol/L 4/ PC is electrolyte, the measured cobalt nanometer V that mixes 2o 5the cyclic voltammetry curve of membrane electrode, as shown in Figure 7, sweeps speed for 10mV/s, and scanning voltage scope is-0.2V～0.6V vs.Ag/AgCl; The measured cobalt nanometer V that mixes 2o 5the constant current charge-discharge curve of membrane electrode is as Fig. 8; Mixing cobalt nanometer V 2o 5on the cyclic voltammetry curve of membrane electrode, have two pairs of obvious redox peaks, with on its constant current charge-discharge curve two pairs charging/discharging voltage platform is consistent stably, show Li +ion is being mixed cobalt nanometer V 2o 5deintercalation process on membrane electrode is carried out in two steps.Mix cobalt nanometer V as anode material for lithium-ion batteries 2o 5thin-film material shows excellent chemical property: under the condition that is 800mA/g in current density, first charge-discharge specific capacity is respectively 693mAh/g, 729mAh/g, and irreversible capacity is 36mAh/g, on average decays to weekly 0.94%, as Fig. 8 and Figure 15 b.
What the present embodiment was prepared mixes cobalt nanometer V 2o 5membrane electrode performance, adopts lithium ion battery to test.Lithium ion battery is mixed cobalt nanometer V with above-mentioned steps (2) gained 2o 5film is anodal, and lithium metal is negative pole, 1M LiPF 6being dissolved in ethyl carbonate/dimethyl carbonate (EC/DMC) is electrolyte solution, and the assembling process of described lithium ion battery carries out in the glove box that is full of argon gas.
What the present embodiment was prepared mixes cobalt nanometer V 2o 5thin-film material is in the time of full battery charging and discharging test, and current density is 687mA/g, voltage range: 2.0～4.3V, charging and discharging capacity is respectively up to 698mAh/g, 710mAh/g, irreversible capacity is 12mAh/g, and in 80 discharge cycles tests, on average decay is only 0.60% weekly, as Figure 16.
Embodiment 2
The related a kind of lithium ion battery of the present embodiment is with mixing cobalt nanometer V 2o 5thin-film electrode material is the product that obtained by the following method, is wherein 2.8% containing cobalt amount, as different from Example 1:
In (1) step, accurately take 0.023g CoSO 47H 2o powder, for preparation contains the V that cobalt amount is 2.8% 2o 5colloidal sol.
The nanometer V that is 2.8% containing cobalt amount that the present embodiment is prepared 2o 5membrane electrode adopts three-electrode system test, and respectively as shown in Figure 9 and Figure 10, under the condition that is 800mA/g in current density, discharge capacity is 662mAh/g, on average decays to weekly 1.15%, as Figure 15 c for cyclic voltammetry curve and constant current charge-discharge curve.Prepared by the present embodiment mixes cobalt nanometer V 2o 5the discharge capacity attenuation curve of membrane electrode under different current densities as shown in figure 17.As can be seen from the figure, in the time that current density is 400mA/g, discharge capacity is 662mAh/g, and while increasing current density to 1000mA/g, discharge capacity is still 658mAh/g, and while again increasing charging and discharging currents density to 8000mA/g, discharge capacity is still 271mAh/g.After 5 circulations, under different current densities, on average decay is respectively 1.08%, 1.18%, 1.14%, 1.77%, 1.31%, 0.91%, 1.31% weekly, is more or less the same, and hence one can see that, and this mixes cobalt nanometer V 2o 5membrane electrode, along with the increase of current density, still has good cycle performance and high rate charge-discharge performance.
Embodiment 3
The related a kind of lithium ion battery of the present embodiment is with mixing manganese nanometer V 2o 5thin-film electrode material is the product that obtained by the following method, and wherein manganese content is 2%, as different from Example 1:
In (1) step, accurately take 0.0076g MnC 2o 4powder, for preparing the V that manganese content is 2.0% 2o 5colloidal sol.
Manganese content is 2.0% nanometer V 2o 5membrane electrode adopts three-electrode system to test, cyclic voltammetry curve as shown in figure 11, current density be charging and discharging curve under 800mA/g condition as shown in figure 12, initial discharge specific capacity can reach 706mAh/g, on average decays to weekly 1.93%, as Figure 15 d.Prepared by the present embodiment mixes manganese nanometer V 2o 5the discharge capacity attenuation curve of membrane electrode under different current densities as shown in figure 18.As can be seen from the figure,, in the time that current density is 800mA/g, discharge capacity is 706mAh/g, while increasing current density to 6000mA/g, discharge capacity is still up to 476mAh/g, and while again increasing charging and discharging currents density to 10000mA/g, discharge capacity is still up to 400mAh/g.After 5 circulations, under different current densities, on average decay is respectively 1.93%, 3.36%, 1.68%, 0.93% weekly, is more or less the same, and hence one can see that, and this mixes manganese nanometer V 2o 5membrane electrode, along with the increase of current density, still has good cycle performance and high rate charge-discharge performance.
Embodiment 4
The related a kind of lithium ion battery of the present embodiment is with mixing nickel nanometer V 2o 5thin-film electrode material is the product that obtained by the following method, and wherein nickel content is 2.0%, as different from Example 1:
In (1) step, accurately take 0.0077g NiSO 4powder, for preparing the V that nickel content is 2.0% 2o 5colloidal sol.
Nickel content is 2.0% nanometer V 2o 5membrane electrode adopts three-electrode system to test, and cyclic voltammetry curve as shown in figure 13, is that charging and discharging curve under 800mA/g condition is as Figure 14 in current density; Initial discharge specific capacity can reach 792mAh/g, on average decays to weekly 1.32%, as Figure 15 e.
Embodiment 5
A kind of lithium ion battery V that the present embodiment is related 2o 5thin-film electrode material is the product that obtained by the following method, as different from Example 1:
In (1) step, only take V 2o 5powder, for preparing pure V 2o 5colloidal sol.
Pure V 2o 5membrane electrode adopts three-electrode system to test, cyclic voltammetry curve as shown in Figure 5, current density be charging and discharging curve under 800mA/g condition as shown in Figure 6; Initial discharge capacity is 625mAh/g, on average decays to weekly 3.23%, as Figure 15 a.

Claims (4)

1. a dopen Nano vanadic oxide thin-film electrode material for lithium ion battery, comprise the combination in any of Co-V oxide, Mn-V oxide, Ni-V oxide or above-mentioned oxide, Co, Mn in described Co-V oxide, Mn-V oxide, Ni-V oxide, Ni element derive from the mixture of a kind of in oxide, hydroxide and salt separately or at least two kinds, it is characterized in that this electrode material is the product obtaining by following preparation method:
(1) doping V 2o 5the preparation of colloidal sol: first take V 2o 5powder and Co, Mn, Ni element come the mixture of a kind of of source compound or at least two kinds, wherein m (Co): m (V 2o 5) be 2.0%～2.8%, m (Mn): m (V 2o 5) be 2.0%, m (Ni): m (V 2o 5) be 2.8%, and both are mixed; Then get the hydrogen peroxide (H of 3mL30% 2o 2) solution is placed in the beaker of 25mL, at room temperature, said mixture added wherein, stir, and then add 2mL deionized water to continue to be stirred to form stable rufous vitreosol, be settled to 100mL, obtain the V that adulterates 2o 5colloidal sol;
(2) dopen Nano V 2o 5the preparation of membrane electrode: the Pt sheet deionized water being immersed in hydrogen peroxide is rinsed well, air-dry; Get the above-mentioned doping V of 10 μ L 2o 5colloidal sol, spreads on the Pt sheet of handling well, under room temperature, after natural air drying, is placed in Muffle furnace and calcines 2 hours at 500 ℃, naturally cools to room temperature, obtains dopen Nano V 2o 5membrane electrode, this nano-electrode material is that length is 500～600nm, and wide is 150～200nm, and thick is the cuboid nanometer sheet of 60～90nm.
2. dopen Nano vanadic oxide thin-film electrode material for a kind of lithium ion battery according to claim 1, is characterized in that: dopen Nano V 2o 5in thin-film electrode material, doped chemical is Co, is that 2.0%～2.8%, Co element derives from CoSO containing cobalt amount 47H 2o.
3. dopen Nano vanadic oxide thin-film electrode material for a kind of lithium ion battery according to claim 1, is characterized in that: dopen Nano V 2o 5in thin-film electrode material, doped chemical is Mn, and manganese content is that 2.0%, Mn element derives from MnC 2o 4.
4. dopen Nano vanadic oxide thin-film electrode material for a kind of lithium ion battery according to claim 1, is characterized in that: dopen Nano V 2o 5in thin-film electrode material, doped chemical is Ni, and nickel content is that 2.8%, Ni element derives from NiSO 4.
CN201410108180.5A 2014-03-21 2014-03-21 Doped nanometer vanadium pentoxide membrane electrode material for lithium ion battery Pending CN103887485A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410108180.5A CN103887485A (en) 2014-03-21 2014-03-21 Doped nanometer vanadium pentoxide membrane electrode material for lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410108180.5A CN103887485A (en) 2014-03-21 2014-03-21 Doped nanometer vanadium pentoxide membrane electrode material for lithium ion battery

Publications (1)

Publication Number Publication Date
CN103887485A true CN103887485A (en) 2014-06-25

Family

ID=50956287

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410108180.5A Pending CN103887485A (en) 2014-03-21 2014-03-21 Doped nanometer vanadium pentoxide membrane electrode material for lithium ion battery

Country Status (1)

Country Link
CN (1) CN103887485A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105375004A (en) * 2015-10-23 2016-03-02 湘潭大学 Lithium secondary battery cathode material with long service life and high energy and preparation method thereof
CN107069020A (en) * 2017-02-17 2017-08-18 武汉理工大学 A kind of preparation method of lithium ion battery nickel doping vanadic anhydride nano-sheet positive electrode
CN110790315A (en) * 2019-02-22 2020-02-14 重庆大学 Preparation method of lithium ion battery anode Li4Mn5O12 nanoparticles
US20210340024A1 (en) * 2018-10-30 2021-11-04 Unist(Ulsan National Institute Of Science And Technology) Ferromagnetic element-substituted room-temperature multiferroic material and method for manfuacturing same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101937993A (en) * 2009-06-30 2011-01-05 比亚迪股份有限公司 Anode material and preparation method thereof and battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101937993A (en) * 2009-06-30 2011-01-05 比亚迪股份有限公司 Anode material and preparation method thereof and battery

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
D.M.YU.ETAL: "Effect of manganese doping on Li-ion intercalation properties of V2O5 films", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 20, 19 September 2010 (2010-09-19) *
YANYI LIU.ETAL: "V2O5 Nano-Electrodes with High Power and Energy Densities for Thin Film Li-ion Batteries", 《ADVANCED ENERGY MATERIALS》, vol. 1, 30 December 2011 (2011-12-30) *
余丹梅: "钒氧化物正极材料的研究现状", 《电池工业》, no. 1, 28 February 2012 (2012-02-28) *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105375004A (en) * 2015-10-23 2016-03-02 湘潭大学 Lithium secondary battery cathode material with long service life and high energy and preparation method thereof
CN105375004B (en) * 2015-10-23 2020-03-31 湘潭大学 Long-life high-energy lithium secondary battery positive electrode material and preparation method thereof
CN107069020A (en) * 2017-02-17 2017-08-18 武汉理工大学 A kind of preparation method of lithium ion battery nickel doping vanadic anhydride nano-sheet positive electrode
CN107069020B (en) * 2017-02-17 2020-06-19 武汉理工大学 Preparation method of nickel-doped vanadium pentoxide nanosheet-shaped positive electrode material for lithium ion battery
US20210340024A1 (en) * 2018-10-30 2021-11-04 Unist(Ulsan National Institute Of Science And Technology) Ferromagnetic element-substituted room-temperature multiferroic material and method for manfuacturing same
US11958758B2 (en) * 2018-10-30 2024-04-16 Unist(Ulsan National Institute Of Science And Technology) Ferromagnetic element-substituted room-temperature multiferroic material and method for manufacturing same
CN110790315A (en) * 2019-02-22 2020-02-14 重庆大学 Preparation method of lithium ion battery anode Li4Mn5O12 nanoparticles

Similar Documents

Publication Publication Date Title
CN102169990B (en) Ternary cathode material and production method thereof
CN107215900B (en) A method of in lithium-rich manganese-based anode material oberbau spinel structure
CN102891309B (en) Preparation method of spherical lithium-enriched anode material with gradient concentration
CN114790013A (en) Sodium ion battery positive electrode active material capable of self-supplementing sodium, and preparation method and application thereof
CN102214819B (en) Method for manufacturing cobalt nickel lithium manganate oxide as gradient anode active material of lithium ion battery
CN104835955B (en) A kind of lithium ion battery nickle cobalt lithium manganate composite positive pole and preparation method thereof
CN105514373A (en) Positive electrode material of high-capacity lithium ion battery and preparation method of positive electrode material
CN103606663B (en) A kind of Multiplying-power lithium-rich composite anode material and preparation method thereof
US20210221702A1 (en) A Lithium-Rich Layered Oxide Material With Phase Structure Gradient And Its Preparation Method
CN103094550A (en) Preparation method of lithium-rich anode material
CN103474646B (en) A kind of mesh structural porous lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof
CN104835957B (en) Preparation method of high-nickel ternary material used for lithium ion battery
CN102916171B (en) Concentration-gradually-changed spherical lithium nickel manganese oxide cathode material and preparation method thereof
EP2784853A1 (en) Lithium transistion metal titanate with a spinel structure, method for its manufacturing, its use, Li-ion cell and battery
CN103794776A (en) High-voltage high-compaction composite positive electrode material of lithium ion battery and preparation method
CN104979549A (en) Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material
CN104157844A (en) High magnifying power lithium-rich manganese-based cathode material with nano/microstructure
CN103078099A (en) Anode material for lithium ion cell and preparation method thereof
CN105024067A (en) Lithium ion battery, composite doping modified positive electrode active material thereof and preparation method
CN104868110A (en) Graphene-oriented mesoporous Co2V2O7 nanosheet material and production method and application thereof
CN103367733A (en) Lithium ion battery cathode material and preparation method thereof and lithium ion battery
Huang et al. Surface modification of hierarchical Li1. 2Mn0. 56Ni0. 16Co0. 08O2 with melting impregnation method for lithium-ion batteries
CN104733725A (en) Application and modified preparation method of manganese and lithium rich solid solution material
Shi et al. Morphology and electrochemical performance of Li [Li0. 2Mn0. 56Ni0. 16Co0. 08] O2 cathode materials prepared with different metal sources
CN103887485A (en) Doped nanometer vanadium pentoxide membrane electrode material for lithium ion battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20140625