CN103985863A - Lithium ion battery positive electrode material composed of cerium oxide and carbon co-coated lithium vanadium phosphate and preparation method thereof - Google Patents
Lithium ion battery positive electrode material composed of cerium oxide and carbon co-coated lithium vanadium phosphate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium ion battery positive electrode material composed of cerium oxide and carbon co-coated lithium vanadium phosphate and a preparation method thereof. According to the preparation method, vanadium pentoxide, citric acid, ammonium biphosphate and lithium carbonate in a mol ratio of 2: 4: 6: 3 are used as raw materials for preparation of carbon coated lithium vanadium phosphate, cerium nitrate hexahydrate is used as a cerium source, and the content of CeO2 accounts for 0.5 to 10% of the mass of lithium vanadium phosphate. The method prepares CeO2 and carbon coated lithium vanadium phosphate by using a pH value-controlled sol-gel process and a polyvinyl alcohol-assisted suspension mixing process so as to overcome the disadvantage of poor charge and discharge performance of a conventional carbon coated lithium vanadium phosphate positive electrode material at a high rate. The method is a simple and low-cost modification method and prepares the lithium ion battery positive electrode material with excellent electrochemical performance.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, particularly relate to a kind of cerium oxide (CeO
2) phosphoric acid vanadium lithium (Li composite modified with carbon (C)
3v
2(PO
4)
3) anode material for lithium-ion batteries and preparation method thereof.
Background technology
Lithium ion battery is owing to having high energy density, good charge-discharge performance and the safe fields such as electric motor car and hybrid electric vehicle that are widely used in.Meanwhile, new type power lithium ion battery has also demonstrated boundless application prospect in fields such as following peak load regulation network, solar energy and wind energy electric power storages.
Outstanding owing to having advantages of, Li transition metal phosphate is paid close attention to widely, wherein to LiFePO 4 (LiFePO
4) carried out a large amount of basic research and application study, enter already the epoch of large-scale commercial application, Li
3v
2(PO
4)
3be the very promising emerging anode material for lithium-ion batteries of generally acknowledging, aspect raising room temperature and the basic chemical property of high temperature, causing very large concern.With LiFePO
4compare the Li of monocline
3v
2(PO
4)
3owing to thering is the advantages such as theoretical capacity is high, operating voltage is high, have extended cycle life, become recently study hotspot.Between 3.0-4.3V, can there is V in phosphoric acid vanadium lithium
3+/ V
4+redox reaction, wherein have two lithium ions can be reversible deviate from and embed, and between 3.0-4.8V, three lithium ions in material can take off embedding completely, and the reversible de-embedding of the 3rd lithium ion makes the theoretical specific discharge capacity of material can reach 197mAh/g.
But with LiFePO
4similar, phosphoric acid vanadium lithium low conductivity has limited its practical application.Its reason is from two aspects: the one, the electronic conductivity between particle is lower, the 2nd, granule interior lithium ion embed and the diffusion rate of deviating from lower.This makes battery capacity attenuation when high current charge-discharge rapid, and high rate capability is poor.In addition, due to lithium ion battery in use, Li
3v
2(PO
4)
3particle often directly contacts with electrolyte, causes it constantly to suffer erosion and makes performance variation gradually.
The research work of having delivered at present mainly comprises cation doping, coated C and high conductivity inorganic material, controls particle size and changes particle shape etc.Improve granule interior intrinsic conduction ability and mainly by ion doping, realize, as adopted Al to carry out the doping of V position [Cho A R, Son J N, Lee Y S, et al.Carbon supported, Al doped-Li
3v
2(PO
4)
3as a high rate cathode material for lithium-ion batteries[J], Journal of Materials Chemistry, 2012,22:6556]; Improve conductivity between particle and mainly by coated with conductive material, realize, as coated C[Huang huan, Shieh-Chieh Yin, Tracy Kerr, et al.Nanostructured composities:a high capacity, fast rate Li
3v
2(PO
4)
3/ carbon cathode for rechargeable lithium batteries[J], Advanced Materials, 2001,14:1525-1528].
The most ripe coated means of research are that carbon is coated at present, and the coated of carbon not only makes the electronic conductivity of material be improved, simultaneously also can crystal grain thinning.But simple carbon is coated to be difficult at Li
3v
2(PO
4)
3particle surface generates continuous, even, complete coating layer.And carbon covering amount is unsuitable excessive, otherwise it can reduce the tap density of positive electrode, thereby reduce the energy density of battery, should reduce the content of carbon as far as possible.We are coated LiFePO altogether to C and the good inorganic compound material of conductivity in laboratory
4do a series of research, mainly contained ZnO, CuO, La
0.7sr
0.3mnO
3, La
0.6sr
0.4coO
3-δ, Sr
0.85ce
0.15coO
3-δ, Ti
3siC
2with TiN etc., find that coated is altogether to improve LiFePO
4the extraordinary method of positive electrode normal temperature chemical property, to improving high rate capability successful.Other scholars are to LiFePO
4research show, C and CeO
2coated to improving LiFePO altogether
4normal temperature [Liu Yan, Mi Changhuan, Zhang Xiaogang, et al.Improvement of electrochemical and thermal stability of LiFePO
4cathode modified by CeO
2[J], Journal of Electroanalytical Chemistry, 2009,628:73-80] and low temperature [Yao Jingwen, Wu Feng, Qiu Xinping, et al.Effect of CeO
2-coating on the electrochemical performances of LiFePO
4/ C cathode material[J], Electrochimica Acta, 2011,56:5587-5592] chemical property has good effect.
In recent years, phosphoric acid vanadium lithium composite modified also had carried out some research to work.Because sol-gal process technique is simple, be easy to synthesize, and the powder particle size synthesizing distribution is less, better performances, so composite modified phosphoric acid vanadium lithium is mainly to be undertaken by sol-gal process.As document has been reported with MgO and C composite modified [Zhai Jing, Zhao Minshou, Wang Dandan, et al.Effect of MgO nanolayer coated on Li
3v
2(PO
4)
3/ C cathode material for lithium-ion battery[J], Journal of Alloys and Compounds, 2010,502:401-406], SiO
2with C composite modified [Zhang Lulu, Liang Gan, Peng Gang, et al.Significantly improved electrochemical performance in Li
3v
2(PO
4)
3/ C promoted by SiO
2coating for lithium-ion batteries[J], The Journal of Physical Chemistry, 2012,116:12401-12408], Ag and composite modified [the Zhang L of C, Wang X L, Tu J P, et al.Synthesis and electrochemical performances of Li
3v
2(PO
4)
3/ (Ag+C) composite cathode[J], Journal of Power Sources, 2010,195:5057 – 5061], adopt altogether the coated positive electrode chemical property that carries out composite modified preparation to have and significantly improve, particularly high rate capability.In addition, regulate the pH value in preparation process, to particle size have clearly improve effect [Xu Wenwen, Liu Li, Guo Haolong, et al.Synthesis and electrochemical properties of Li
3v
2(PO
4)
3/ C cathode material with an improved sol – gel method by changing pH value[J], Electrochimica Acta, 2013,113:497-505].
By literature search, of the present inventionly for phosphoric acid vanadium lithium, adopt coated carrying out to be altogether composite modifiedly not yet disclosed and to report.
Summary of the invention
Object of the present invention, is to adopt sol-gal process and the auxiliary legal preparation of the suspended mixture CeO of polyvinyl alcohol that controls pH value
2be coated altogether phosphoric acid vanadium lithium with carbon, to improve the coated poor shortcoming of vanadium phosphate cathode material high-rate charge-discharge capability of existing carbon.The present invention is a kind of technique method of modifying simple, with low cost, and a kind of anode material for lithium-ion batteries with good electric chemical property is provided.
Anode material for lithium-ion batteries high-rate charge-discharge capability poor because have a lot of aspects, as low in electrolyte ion conductance, on electrode, form solid electrolyte interface film (SEI), polarization, electrode electrolyte interface charge transfer resistance that lithium ion diffusion coefficient is low, high are high.In addition, poor, the difficulty of the transmission by diaphragm material of wetability and other battery design features are also the poor reasons of chemical property.
The present invention is 4 by regulating pH value in sol-gel process, makes that the coated phosphoric acid vanadium lithium material granule of synthetic carbon is tiny, particle size distribution range is narrow, and the germination of C layer obstruction also provides good electrically contacting between particle, the CeO of existence
2repair incomplete C network, this coating layer not only provides high conductivity nanometer layer between particle, make particle have low charge transfer resistance and high conductivity, and has hindered direct contact the between particle and electrolyte, has reduced particle by the corrosion of electrolyte.Be coated and reduced the particularly capacitance loss of high charge-discharge magnification altogether, interface resistance and anodal polarization reduce obvious.And complexing agent citric acid can, directly as carbon source and reducing agent, need not add another kind of material as carbon source or reducing agent.In addition, pH value is the key factor that affects sol-gal process, and it will directly affect the hydrolysis degree of reactant, polymerization methods and end product.The powder characteristic of the presoma sintering obtaining under different pH condition after is out not identical yet.Therefore the present invention, exactly by pH value is adjusted to 4, adds citric acid and carries out CeO
2with C be coated altogether modified anode material phosphoric acid vanadium lithium.
Technical solution of the present invention is as follows:
Cerium oxide and carbon is an anode material for lithium-ion batteries for coated phosphoric acid vanadium lithium altogether, and its composition and quality percentage composition are as follows:
Adopting vanadic oxide, citric acid, ammonium dihydrogen phosphate, lithium carbonate is raw material, and its mol ratio is 2:4:6:3, prepares the coated phosphoric acid vanadium lithium of carbon; Take six water cerous nitrates as cerium source, CeO
2it is 0.5～10% that content accounts for phosphoric acid vanadium lithium mass percent;
Described cerium oxide and carbon is the anode material for lithium-ion batteries of coated phosphoric acid vanadium lithium altogether, adopts sol-gal process and auxiliary legal being prepared of suspended mixture of polyvinyl alcohol of controlling pH value, and step is as follows:
(1) after citric acid being dissolved in 20mL deionized water, add vanadium pentoxide powder, the mol ratio of vanadic oxide and citric acid is 1:2; On magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes, form dark blue solution;
(2) ammonium dihydrogen phosphate and lithium carbonate are dissolved in respectively in 20mL deionized water, then pour in the dark blue solution of step (1), mole metering of ammonium dihydrogen phosphate, lithium carbonate, vanadic oxide is than being 6:3:2; With acetic acid, join in dark blue solution, regulating pH value is 4; Be placed in magnetic force heating stirrer and under 60 ℃ of constant temperature, continue to stir 1 hour, then be warming up to 80 ℃ of evaporating solvents, form wet gel; Again wet gel is put into the baking oven of 80 ℃, within standing 1 day, formed xerogel, after grinding, obtain blue-green powder;
(3) the blue-green powder of step (2) is put into quartz tube furnace, pass into the hydrogen-nitrogen mixture gas that hydrogen content is 5% volume ratio, in 350 ℃ of insulations 5 hours, be warming up to afterwards 750 ℃ of insulations 8 hours, naturally cool to room temperature; After grinding, sieving, obtain the coated vanadium-lithium phosphate powder for lithium of carbon;
(4) the coated vanadium-lithium phosphate powder for lithium of the carbon of step (3) and six water cerous nitrates are weighed by a certain percentage to CeO
2it is 0.5～10% that content accounts for phosphoric acid vanadium lithium mass percent; The coated vanadium-lithium phosphate powder for lithium of carbon is distributed to and in deionized water, forms suspension, six water cerous nitrates are dissolved in and in deionized water, form solution, wherein in the coated phosphoric acid vanadium lithium suspension of carbon, adding mass fraction is 0.5% poly-vinyl alcohol solution sonic oscillation after 20 minutes, stirs 3 hours under room temperature;
(5) step (4) gained six water cerous nitrate solutions are dropwise joined in the coated phosphoric acid vanadium lithium suspension of carbon, under room temperature, continue to stir 3 hours, then under the heating condition of 60 ℃, stir after 1 hour and be warmed up to 80 ℃ of continuation stirrings until water evaporates obtains pastel;
(6) step (5) gained pastel is put into baking oven, at 80 ℃, be dried 12 hours, ground afterwards 280 mesh sieves, obtain black powder;
(7) the black powder after step (6) is sieved is placed in tube furnace, and in argon atmospher, 650 ℃ of heat treatment is 5 hours, again grinds, sieves, and obtains cerium oxide and the carbon anode material for lithium-ion batteries of coated phosphoric acid vanadium lithium altogether.
The citric acid of described step (1) is simultaneously as complexing agent, reducing agent and carbon source.
The polyvinyl alcohol of described step (4) is pattern controlling agent and dispersant.
The present invention adopts and controls the sol-gal process of pH value and the auxiliary suspended mixture of polyvinyl alcohol is legal, prepares carbon and is coated phosphoric acid vanadium lithium and carries out CeO
2coated, obtained CeO
2be coated altogether vanadium-lithium phosphate powder for lithium with C, prepared the anode material for lithium-ion batteries with good electric chemical property.Citric acid, simultaneously as complexing agent, reducing agent and carbon source, has been saved production cost.Preparation method's technique of the present invention is simple, and material electrochemical performance is excellent, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 to 3 is schemed with comparative example's powder x-ray diffraction (XRD);
Fig. 2 be the embodiment of the present invention 1 to 3 with comparative example's 0.2 multiplying power under discharge curve first;
Fig. 3 be the embodiment of the present invention 1 to 3 with comparative example's 5 multiplying powers under cycle performance curve chart;
Fig. 4 is the XRD comparison diagram of the powder of the embodiment of the present invention 2;
Fig. 5 is the energy spectrogram of the embodiment of the present invention 2.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Comparative example
4.145g citric acid is dissolved in 20mL deionized water, pours in the beaker that 1.803g vanadic oxide is housed, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes, form dark blue solution.3.421g ammonium dihydrogen phosphate and 1.121g lithium carbonate are dissolved in respectively in 20mL deionized water, join in above-mentioned dark blue solution, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes.With second acid for adjusting pH value to 4, mixing material 60 ℃ of constant temperature on magnetic force heating stirrer are stirred 1 hour.Be warming up to 80 ℃, continue stirring and make solvent evaporation form navy blue wet gel, put into 80 ℃ of baking ovens and within standing 1 day, form xerogel.Xerogel is to blue-green in 30 minutes with mortar grinding Powdered.By the 350 ℃ of insulations 4 hours under the hydrogen-nitrogen mixture gas of hydrogeneous 5% (volume ratio) of blue-green powder, get rid of ammonia and steam etc. again.Be warming up to afterwards 750 ℃ of insulations 8 hours, naturally cool to room temperature, powder grinding is crossed to 280 mesh sieves after 1 hour, can obtain the coated phosphoric acid vanadium lithium of carbon (not having cerium oxide to be coated) goods.
Using the coated phosphoric acid vanadium lithium powder of this carbon as positive electrode, adopt conventional method to be assembled into button cell, then carry out electrochemical property test.
The coated vanadium-lithium phosphate powder for lithium material of carbon is carried out XRD test and battery is carried out to high rate performance and cycle performance test.Comparing with pure phase phosphoric acid vanadium lithium as can be known from Fig. 1, there is not dephasign in sample prepared by comparative example; The sample first discharge specific capacity that under 0.2 multiplying power prepared by comparative example is as can be known from Fig. 2 155.9mAh/g, and efficiency is 79.1% first; The capability retention that the sample that under 5 multiplying powers prepared by comparative example as can be known from Fig. 3 circulates after 100 times is 60.0%.From test result, can find out that there is no the cycle performance of the coated vanadium-lithium phosphate powder for lithium of cerium oxide bad, capacitance loss is very serious.
Embodiment 1
4.145g citric acid is dissolved in 20mL deionized water, pours in the beaker that 1.803g vanadic oxide is housed, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes, form dark blue solution.3.421g ammonium dihydrogen phosphate and 1.121g lithium carbonate are dissolved in respectively in 20mL deionized water, join in above-mentioned dark blue solution, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes.With second acid for adjusting pH value to 4, mixing material 60 ℃ of constant temperature on magnetic force heating stirrer are stirred 1 hour.Be warming up to 80 ℃, continue stirring and make solvent evaporation form navy blue wet gel, put into 80 ℃ of baking ovens and within standing 1 day, form xerogel.Xerogel is to blue-green in 30 minutes with mortar grinding Powdered.By the 350 ℃ of insulations 4 hours under the hydrogen nitrogen mixed gas of hydrogeneous 5% (volume ratio) of blue-green powder, get rid of the gases such as ammonia and steam again.Be warming up to afterwards 750 ℃ of insulations 8 hours, naturally cool to room temperature, powder grinding is crossed to 280 mesh sieves after 1 hour, can obtain the coated phosphoric acid vanadium lithium goods of carbon.The coated vanadium-lithium phosphate powder for lithium of the 4g carbon obtaining is distributed in 100mL deionized water and forms suspension, add the PVA solution sonic oscillation of 2mL mass fraction 0.5% under room temperature, to stir 3 hours after 20 minutes.Taking 0.103g six water cerous nitrates is dissolved in 25mL deionized water and forms solution, then dropwise join in the coated phosphoric acid vanadium lithium suspension of carbon, under room temperature, continue to stir 3 hours, then under the heating condition of 60 ℃, stir after 1 hour and be warmed up to 80 ℃ of continuation stirrings until water evaporates obtains pastel.Again the pastel obtaining is put at 80 ℃, baking oven dry 12 hours, ground afterwards and within 30 minutes, cross 280 mesh sieves and obtain black powder.Again black powder is placed in to tube furnace, under argon atmospher, 650 ℃ of heat treatment is 5 hours, grinds and crosses 280 mesh sieves in 1 hour, and obtaining mass fraction is 1%CeO
2be coated altogether the anode material for lithium-ion batteries of phosphoric acid vanadium lithium with carbon.
With this CeO
2as positive electrode, adopt conventional method to be assembled into button cell with the coated phosphoric acid vanadium lithium powder of carbon, then carry out electrochemical property test.
Powder body material is carried out XRD test and battery is carried out to high rate performance and cycle performance test.Compare with pure phase phosphoric acid vanadium lithium as can be known from Fig. 1, the height of specimen crystallization of embodiment 1 preparation, principal crystalline phase is phosphoric acid vanadium lithium; Under 0.2 multiplying power, the sample first discharge specific capacity of embodiment 1 preparation is 156.0mAh/g as can be known from Fig. 2, and efficiency is 79.2% first; The capability retention that under 5 multiplying powers, the sample of embodiment 1 preparation circulates after 100 times is as can be known from Fig. 3 89.3%.Can find out, carry out 1%CeO
2after coated, cycle performance improves obviously.
Embodiment 2
4.145g citric acid is dissolved in 20mL deionized water, pours in the beaker that 1.803g vanadic oxide is housed, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes, form dark blue solution.3.421g ammonium dihydrogen phosphate and 1.121g lithium carbonate are dissolved in respectively in 20mL deionized water, join in above-mentioned dark blue solution, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes.With second acid for adjusting pH value to 4, mixing material 60 ℃ of constant temperature on magnetic force heating stirrer are stirred 1 hour.Be warming up to 80 ℃, continue stirring and make solvent evaporation form navy blue wet gel, put into 80 ℃ of baking ovens and within standing 1 day, form xerogel.Xerogel is to blue-green in 30 minutes with mortar grinding Powdered.By the 350 ℃ of insulations 4 hours under the hydrogen nitrogen mixed gas of hydrogeneous 5% (volume ratio) of blue-green powder, get rid of the gases such as ammonia and steam again.Be warming up to afterwards 750 ℃ of insulations 8 hours, naturally cool to room temperature, powder grinding is crossed to 280 mesh sieves after 1 hour, can obtain the coated phosphoric acid vanadium lithium goods of carbon.The coated vanadium-lithium phosphate powder for lithium of the 4g carbon obtaining is distributed in 100mL deionized water and forms suspension, add the PVA solution sonic oscillation of 2mL mass fraction 0.5% under room temperature, to stir 3 hours after 20 minutes.Taking 0.208g six water cerous nitrates is dissolved in 25mL deionized water and forms solution, then dropwise join in the coated phosphoric acid vanadium lithium suspension of carbon, under room temperature, continue to stir 3 hours, then under the heating condition of 60 ℃, stir after 1 hour and be warmed up to 80 ℃ of continuation stirrings until water evaporates obtains pastel.The pastel obtaining is put at 80 ℃, baking oven dry 12 hours, ground afterwards and within 30 minutes, cross 280 mesh sieves and obtain black powder.Again black powder is placed in to tube furnace, under argon atmospher, 650 ℃ of heat treatment is 5 hours, grinds and crosses 280 mesh sieves in 1 hour, and obtaining mass fraction is 2%CeO
2be coated altogether the anode material for lithium-ion batteries of phosphoric acid vanadium lithium with carbon.
With this CeO
2as positive electrode, adopt conventional method to be assembled into button cell with the coated phosphoric acid vanadium lithium powder of carbon, then carry out electrochemical property test.
Powder body material is carried out XRD and EDS test and battery is carried out to high rate performance and cycle performance test.Compare with pure phase phosphoric acid vanadium lithium as can be known from Fig. 1, the height of specimen crystallization of embodiment 3 preparations, principal crystalline phase is phosphoric acid vanadium lithium; Under 0.2 multiplying power, the sample first discharge specific capacity of embodiment 2 preparations is 155.9mAh/g as can be known from Fig. 2, and efficiency is 79.2% first; The capability retention that under 5 multiplying powers, the sample of embodiment 2 preparations circulates after 100 times is as can be known from Fig. 3 93.5%; From the XRD comparison diagram of Fig. 4, can find out, there is the diffraction maximum of ceria in the sample of embodiment 2 preparations; In the sample of embodiment 2 preparations, there is Ce element as can be seen from Figure 5.From test result, can find out and carry out 2%CeO
2after coated, cycle performance has obtained significantly improving.
Embodiment 3
4.145g citric acid is dissolved in 20mL deionized water, pours in the beaker that 1.803g vanadic oxide is housed, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes, form dark blue solution.3.421g ammonium dihydrogen phosphate and 1.121g lithium carbonate are dissolved in respectively in 20mL deionized water, join in above-mentioned dark blue solution, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes.With second acid for adjusting pH value to 4, mixing material 60 ℃ of constant temperature on magnetic force heating stirrer are stirred 1 hour.Be warming up to 80 ℃, continue stirring and make solvent evaporation form navy blue wet gel, put into 80 ℃ of baking ovens and within standing 1 day, form xerogel.Xerogel is to blue-green in 30 minutes with mortar grinding Powdered.By the 350 ℃ of insulations 4 hours under the hydrogen nitrogen mixed gas of hydrogeneous 5% (volume ratio) of blue-green powder, get rid of the gases such as ammonia and steam again.Be warming up to afterwards 750 ℃ of insulations 8 hours, naturally cool to room temperature, powder grinding is crossed to 280 mesh sieves after 1 hour, can obtain the coated phosphoric acid vanadium lithium goods of carbon.The coated vanadium-lithium phosphate powder for lithium of the 4g carbon obtaining is distributed in 100mL deionized water and forms suspension, add the PVA solution sonic oscillation of 2mL mass fraction 0.5% under room temperature, to stir 3 hours after 20 minutes.Taking 0.315g six water cerous nitrates is dissolved in 25mL deionized water and forms solution, then dropwise join in the coated phosphoric acid vanadium lithium suspension of carbon, under room temperature, continue to stir 3 hours, then under the heating condition of 60 ℃, stir after 1 hour and be warmed up to 80 ℃ of continuation stirrings until water evaporates obtains pastel.The pastel obtaining is put at 80 ℃, baking oven dry 12 hours, ground afterwards and within 30 minutes, cross 280 mesh sieves and obtain black powder.Again black powder is placed in to tube furnace, under argon atmospher, 650 ℃ of heat treatment is 5 hours, grinds and crosses 280 mesh sieves in 1 hour, and obtaining mass fraction is 3%CeO
2be coated altogether the anode material for lithium-ion batteries of phosphoric acid vanadium lithium with carbon.
With this CeO
2as positive electrode, adopt conventional method to be assembled into button cell with the coated phosphoric acid vanadium lithium powder of carbon, then carry out electrochemical property test.
Powder body material is carried out XRD test and battery is carried out to high rate performance and cycle performance test.Compare with pure phase phosphoric acid vanadium lithium as can be known from Fig. 1, the height of specimen crystallization of embodiment 3 preparations, principal crystalline phase is phosphoric acid vanadium lithium; Under 0.2 multiplying power, the sample first discharge specific capacity of embodiment 3 preparations is 151.8mAh/g as can be known from Fig. 2, and efficiency is 77.1% first; The capability retention that under 5 multiplying powers, the sample of embodiment 3 preparations circulates after 100 times is as can be known from Fig. 3 84.9%.Result shows to carry out 3%CeO
2although after coated, under low range, first charge-discharge declines to some extent, is improved largely aspect cycle performance.
Embodiment 4
4.145g citric acid is dissolved in 20mL deionized water, pours in the beaker that 1.803g vanadic oxide is housed, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes, form dark blue solution.3.421g ammonium dihydrogen phosphate and 1.121g lithium carbonate are dissolved in respectively in 20mL deionized water, join in above-mentioned dark blue solution, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes.With second acid for adjusting pH value to 4, mixing material 60 ℃ of constant temperature on magnetic force heating stirrer are stirred 1 hour.Be warming up to 80 ℃, continue stirring and make solvent evaporation form navy blue wet gel, put into 80 ℃ of baking ovens and within standing 1 day, form xerogel.Xerogel is to blue-green in 30 minutes with mortar grinding Powdered.By the 350 ℃ of insulations 4 hours under the hydrogen nitrogen mixed gas of hydrogeneous 5% (volume ratio) of blue-green powder, get rid of the gases such as ammonia and steam again.Be warming up to afterwards 750 ℃ of insulations 8 hours, naturally cool to room temperature, powder grinding is crossed to 280 mesh sieves after 1 hour, can obtain the coated phosphoric acid vanadium lithium goods of carbon.The coated vanadium-lithium phosphate powder for lithium of the 4g carbon obtaining is distributed in 100mL deionized water and forms suspension, add the PVA solution sonic oscillation of 2mL mass fraction 0.5% under room temperature, to stir 3 hours after 20 minutes.Taking 1.133g six water cerous nitrates is dissolved in 25mL deionized water and forms solution, then dropwise join in the coated phosphoric acid vanadium lithium suspension of carbon, under room temperature, continue to stir 3 hours, then under the heating condition of 60 ℃, stir after 1 hour and be warmed up to 80 ℃ of continuation stirrings until water evaporates obtains pastel.The pastel obtaining is put at 80 ℃, baking oven dry 12 hours, ground afterwards and within 30 minutes, cross 280 mesh sieves and obtain black powder.Again black powder is placed in to tube furnace, under argon atmospher, 650 ℃ of heat treatment is 5 hours, grinds and crosses 280 mesh sieves in 1 hour, and obtaining mass fraction is 10%CeO
2be coated altogether the anode material for lithium-ion batteries of phosphoric acid vanadium lithium with carbon.
With this CeO
2as positive electrode, adopt conventional method to be assembled into button cell with the coated phosphoric acid vanadium lithium powder of carbon, then carry out electrochemical property test.Battery is carried out to high rate performance, cycle performance and ac impedance measurement.It is very unobvious that result shows that chemical property improves.
Embodiment 5
4.145g citric acid is dissolved in 20mL deionized water, pours in the beaker that 1.803g vanadic oxide is housed, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes, form dark blue solution.3.421g ammonium dihydrogen phosphate and 1.121g lithium carbonate are dissolved in respectively in 20mL deionized water, join in above-mentioned dark blue solution, on magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes.With second acid for adjusting pH value to 4, mixing material 60 ℃ of constant temperature on magnetic force heating stirrer are stirred 1 hour.Be warming up to 80 ℃, continue stirring and make solvent evaporation form navy blue wet gel, put into 80 ℃ of baking ovens and within standing 1 day, form xerogel.Xerogel is to blue-green in 30 minutes with mortar grinding Powdered.By the 350 ℃ of insulations 4 hours under the hydrogen nitrogen mixed gas of hydrogeneous 5% (volume ratio) of blue-green powder, get rid of the gases such as ammonia and steam again.Be warming up to afterwards 750 ℃ of insulations 8 hours, naturally cool to room temperature, powder grinding is crossed to 280 mesh sieves after 1 hour, can obtain the coated phosphoric acid vanadium lithium goods of carbon.The coated vanadium-lithium phosphate powder for lithium of the 4g carbon obtaining is distributed in 100mL deionized water and forms suspension, add the PVA solution sonic oscillation of 2mL mass fraction 0.5% under room temperature, to stir 3 hours after 20 minutes.Taking 0.051g six water cerous nitrates is dissolved in 25mL deionized water and forms solution, then dropwise join in the coated phosphoric acid vanadium lithium suspension of carbon, under room temperature, continue to stir 3 hours, then under the heating condition of 60 ℃, stir after 1 hour and be warmed up to 80 ℃ of continuation stirrings until water evaporates obtains pastel.Again the pastel obtaining is put at 80 ℃, baking oven dry 12 hours, ground afterwards and within 30 minutes, cross 280 mesh sieves and obtain black powder.Again black part body is placed in to tube furnace, under argon atmospher, 650 ℃ of heat treatment is 5 hours, grinds and crosses 280 mesh sieves in 1 hour, and obtaining mass fraction is 0.5%CeO
2be coated altogether the anode material for lithium-ion batteries of phosphoric acid vanadium lithium with carbon.
With this CeO
2as positive electrode, adopt conventional method to be assembled into button cell with the coated phosphoric acid vanadium lithium powder of carbon, then carry out electrochemical property test.Battery is carried out to high rate performance, cycle performance and ac impedance measurement.Result shows that chemical property makes moderate progress.
Method of testing of the present invention is as follows.
The CeO making with the present invention
2be coated altogether phosphoric acid vanadium lithium powder as active material with C, acetylene black is conductive agent, 66.3% ptfe emulsion (PTFE) is binding agent, 80:15:5 weighs a certain amount of above-mentioned three kinds of materials in mass ratio, be scattered in absolute ethyl alcohol, sonic oscillation 15 minutes, is then stirred to agglomeratingly repeatedly, presses the film for 140 microns of thickness on two roller roll forming machines.By this film at 130 ℃ dry 30 minutes, then from film, go out the positive plate of 10 millimeters of diameters standby.
In the present invention, all test batteries all adopt 2430 type button cells.Battery assembles in the glove box (relative humidity <2%) of high-purity argon gas atmosphere.The barrier film using in assembling process is Celgard2400 microporous polypropylene membrane, and electrolyte is 1mol/L LiPF
6ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed liquor (volume ratio of EC and DMC is 1:1).Adopting lithium sheet (manufacture of Beijing non-ferrous metal research institute) is negative pole.The upper and lower cover that assembled battery is used and pad are dried after all will cleaning up with alcohol in advance.For removing air and the moisture of all thing adsorptions, before assembling battery, all things are placed in to glove box more than 4 hours.The concrete assembling process of battery is: in the glove box of relative humidity <2%, first with tweezers, positive electrode disk is placed on to the central authorities of lower cover, add appropriate electrolyte, then put into successively barrier film, lithium sheet, make it be placed in middle position, finally putting into pad compresses, build upper cover, be assembled into simulated battery.The simulated battery installing is put into battery special purpose copper mold, with spanner, tighten, make the battery sealing that is hedged off from the outer world.With sample sack, seal interface, the simulated battery installing is shifted out to glove box.
Use high accuracy battery Performance Test System (Shenzhen new Weir Electronics Co., Ltd.) battery to be carried out to the test (voltages: 3.0～4.8V) such as high rate performance, cycle performance.Discharge and recharge system as follows: (1) standing 1 minute; (2) constant current charge is to 4.8V; (3) standing 1 minute; (4) constant current discharge is to 3.0V.Before test, for making the button cell of new assembling reach stable state, need to place and within 24 hours, carry out again above charge-discharge test.
The present invention proposes passes through to control pH value sol-gal process and the auxiliary legal anode material for lithium-ion batteries CeO for preparing of suspended mixture of polyvinyl alcohol
2be coated altogether phosphoric acid vanadium lithium with carbon, by above-described embodiment, be described, person skilled obviously can be changed content as herein described or suitably change and combination within not departing from content of the present invention, spirit and scope, realizes the present invention.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and content.
Claims (3)
1. cerium oxide and carbon are coated an anode material for lithium-ion batteries for phosphoric acid vanadium lithium altogether, and its composition and quality percentage composition are as follows:
Adopting vanadic oxide, citric acid, ammonium dihydrogen phosphate, lithium carbonate is raw material, and its mol ratio is 2:4:6:3, prepares the coated phosphoric acid vanadium lithium of carbon; Take six water cerous nitrates as cerium source, CeO
2it is 0.5～10% that content accounts for phosphoric acid vanadium lithium mass percent;
Described cerium oxide and carbon is the anode material for lithium-ion batteries of coated phosphoric acid vanadium lithium altogether, adopts sol-gal process and auxiliary legal being prepared of suspended mixture of polyvinyl alcohol of controlling pH value, and step is as follows:
(1) after citric acid being dissolved in 20mL deionized water, add vanadium pentoxide powder, the mol ratio of vanadic oxide and citric acid is 1:2; On magnetic force heating stirrer, 60 ℃ of stirrings of constant temperature are 30 minutes, form dark blue solution;
(2) ammonium dihydrogen phosphate and lithium carbonate are dissolved in respectively in 20mL deionized water, then pour in the dark blue solution of step (1), mole metering of ammonium dihydrogen phosphate, lithium carbonate, vanadic oxide is than being 6:3:2; With acetic acid, join in dark blue solution, regulating pH value is 4; Be placed in magnetic force heating stirrer and under 60 ℃ of constant temperature, continue to stir 1 hour, then be warming up to 80 ℃ of evaporating solvents, form wet gel; Again wet gel is put into the baking oven of 80 ℃, within standing 1 day, formed xerogel, after grinding, obtain blue-green powder;
(3) the blue-green powder of step (2) is put into quartz tube furnace, pass into the hydrogen-nitrogen mixture gas that hydrogen content is 5% volume ratio, in 350 ℃ of insulations 5 hours, be warming up to afterwards 750 ℃ of insulations 8 hours, naturally cool to room temperature; After grinding, sieving, obtain the coated vanadium-lithium phosphate powder for lithium of carbon;
(4) the coated vanadium-lithium phosphate powder for lithium of the carbon of step (3) and six water cerous nitrates are weighed by a certain percentage to CeO
2it is 0.5～10% that content accounts for phosphoric acid vanadium lithium mass percent; The coated vanadium-lithium phosphate powder for lithium of carbon is distributed to and in deionized water, forms suspension, six water cerous nitrates are dissolved in and in deionized water, form solution, wherein in the coated phosphoric acid vanadium lithium suspension of carbon, adding mass fraction is 0.5% poly-vinyl alcohol solution sonic oscillation after 20 minutes, stirs 3 hours under room temperature;
(5) step (4) gained six water cerous nitrate solutions are dropwise joined in the coated phosphoric acid vanadium lithium suspension of carbon, under room temperature, continue to stir 3 hours, then under the heating condition of 60 ℃, stir after 1 hour and be warmed up to 80 ℃ of continuation stirrings until water evaporates obtains pastel;
(6) step (5) gained pastel is put into baking oven, at 80 ℃, be dried 12 hours, ground afterwards 280 mesh sieves, obtain black powder;
(7) the black powder after step (6) is sieved is placed in tube furnace, and in argon atmospher, 650 ℃ of heat treatment is 5 hours, again grinds, sieves, and obtains cerium oxide and the carbon anode material for lithium-ion batteries of coated phosphoric acid vanadium lithium altogether.
2. cerium oxide according to claim 1 and carbon are coated the anode material for lithium-ion batteries of phosphoric acid vanadium lithium altogether, it is characterized in that, the citric acid of described step (1) is simultaneously as complexing agent, reducing agent and carbon source.
3. the anode material for lithium-ion batteries of cerium oxide according to claim 1 and the composite modified phosphoric acid vanadium lithium of carbon, is characterized in that, the polyvinyl alcohol of described step (4) is pattern controlling agent and dispersant.
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| CN106252641B (en) * | 2016-10-26 | 2018-11-27 | 福州大学 | Ternary cathode material of lithium ion battery and preparation method are covered in carbon and ceria double-contracting |
| CN107910510A (en) * | 2017-10-31 | 2018-04-13 | 华南理工大学 | A kind of metavanadic acid cerium negative material of lithium ion battery and preparation method and application |
| CN107910510B (en) * | 2017-10-31 | 2020-06-19 | 华南理工大学 | Cerium metavanadate negative electrode material of lithium ion battery and preparation method and application thereof |
| CN108963206B (en) * | 2018-06-14 | 2021-03-19 | 渤海大学 | V for positive electrode of potassium-sulfur battery2O5Preparation method of/S/PVA composite material and electrode plate thereof |
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| CN109860539A (en) * | 2018-12-19 | 2019-06-07 | 中科廊坊过程工程研究院 | A kind of compound phosphoric acid vanadium lithium anode material and its preparation method and application |
| CN109860539B (en) * | 2018-12-19 | 2021-05-28 | 中科廊坊过程工程研究院 | Composite lithium vanadium phosphate cathode material and preparation method and application thereof |
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| CN110085854B (en) * | 2019-06-05 | 2020-12-22 | 骆驼集团武汉光谷研发中心有限公司 | Lithium vanadium phosphate cathode material and preparation method thereof |
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