CN107845801A - A kind of fluorophosphoric acid cobalt lithium anode material of modified synergic and preparation method thereof - Google Patents

A kind of fluorophosphoric acid cobalt lithium anode material of modified synergic and preparation method thereof Download PDF

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CN107845801A
CN107845801A CN201711113068.0A CN201711113068A CN107845801A CN 107845801 A CN107845801 A CN 107845801A CN 201711113068 A CN201711113068 A CN 201711113068A CN 107845801 A CN107845801 A CN 107845801A
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常彩云
冯季军
姜鑫宇
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University of Jinan
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Abstract

The present invention relates to fluorophosphoric acid cobalt lithium anode material of a kind of doping of nickel and carbon/coated with silica modified synergic and preparation method thereof.Preparation process：（1）The lithium source of certain stoichiometric proportion, cobalt source, Fluorine source and nickel source compound are separately added into deionized water, stirred, a certain amount of phosphate radical source compound is added into above-mentioned solution, continue to stir, after transferring them to the reaction of autoclave airtight heating, natural cooling, take out, dry, obtain presoma；（2）By obtained presoma and carbon-source cpd mixed grinding, the calcining under an inert atmosphere through two stages, the Li that carbon-coating nickel adulterates is obtained2Co1‑ x Ni x PO4F/C materials；（3）A certain amount of silica is weighed in beaker, deionized water is added, ultrasound, adds foregoing Li2Co1‑ x Ni x PO4F/C materials, stir, dry, grinding, obtain Li2Co1‑ x Ni x PO4F/C+SiO2Target material.Material granule prepared by the present invention is uniform, good crystallinity, has higher specific capacity and good cycle performance, and synthesis technique is simple and easy to do, and production cost is low.

Description

A kind of fluorophosphoric acid cobalt lithium anode material of modified synergic and preparation method thereof
Technical field
The present invention relates to a kind of positive electrode and its preparation, more particularly to a kind of doping of nickel and carbon/coated with silica association With modified fluorophosphoric acid cobalt lithium anode material and preparation method thereof, belong to technical field of lithium ion.
Background technology
In recent years, the compound polyanionic fluorophosphoric acid cobalt lithium (Li of emerging three-dimensional frame structure2CoPO4F) material is because of tool There is the F compared with strong electronegativity-The PO of ion and strong inductive effect4 3-Ion, and show high oxidation-reduction potential (4.9 V vs. Li+/ Li) and good structural stability, due to containing two Li in the material+, its theoretical capacity is up to 287 mAh g-1, Energy density can reach 1435 Wh kg-1, it is expected to as following exploitation focus.However, the ion of difference, electronic conductivity and following Ring performance is to hinder the wide variety of key factor of this material.
At present, various countries researcher is modified in optimization polyanionic method for preparing anode material and to it aspect progress Many researchs.The measure of generally use has the control to particle size and pattern, three kinds of methods of doping and cladding.(1) control The size that makes pellet and pattern can use different preparation methods to realize.Dumont-Bott etc. uses spark plasma sintering Method realizes control Li in the short period of time, by the approach quickly heated2CoPO4Purpose (the E. of F material particles sizes Dumont-Botto, C. Bourbon, S. Patoux, P. Rozier, M. Dolle. Synthesis by Spark Plasma Sintering: A new way to obtain electrode materials for lithium ion batteries. Journal of Power Sources 196 (2011) 2274-2278).But material prepared by the method Material contains dephasign, and is not easy batch and prepares material.(2) doped metal ion is that another kind effectively improves material electrochemical performance Method.Khasanova etc. in Co positions doped metal ion (Fe, Mn) by improving Li2CoPO4Electric conductivity inside F particles (N.R. Khasanova, O.A. Drozhzhin, S.S. Fedotov, D.A. Storozhilova, R.V. Panin, E.V. Antipov. Synthesis and electrochemical performance of Li2Co1-x M x PO4F (M= Fe, Mn) cathode materials. Beilstein Journal of Nanotechnology 4 (2013) 860- 867).In Li2CoPO4F Co positions incorporation extraneous element, substitutes the cobalt in original lattice, lattice is produced distortion or produces hole Etc. lattice defect is formed, Li can be improved to a certain extent2CoPO4F ion and electron conduction.But due to incorporation member Element is not involved in redox reaction, the cost that materials theory capacity can be brought to reduce.(3) carbon coating is to study more ripe cladding One of method.With regard to LiFePO4For, researcher adds carbon in its preparation process can not only improve its chemical property, and And also act as discrete particles, prevent the effect such as reunion.But the density due to carbon in itself is relatively low, coats excessive carbon and improving Also its tap density can be reduced while material conductivity.Therefore, the addition of carbon should not be excessive while electric conductivity is ensured. Moreover, the effect of carbon materials cladding, which essentially consists in, improves intergranular electric transmission, but excessive carbon coating be unfavorable for lithium from Son, to the transmission of material internal, positive work can not be played to same crucial ionic conductivity in electrochemical reaction from electrolyte With.Oxide cladding can form the pernicious interaction of protective layer prevention material and electrolyte in material surface, so as to improve Structural stability of the material during charge and discharge cycles.Amaresh etc. uses two step Solid phase synthesis Li2CoPO4F, then use ZrO2Coating modification (S. Amaresh, K. Karthikeyan, K. J. Kim, J. Y. An, S. J. is carried out to it Cho, K. Y. Chung, B. W. Cho, K. W. Nam, and Y. S. Lee, Metal Oxide Coated Lithium Cobalt Fluorophosphate Cathode Materials for Lithium Secondary Batteries—Effect of Aging and Temperature. Journal of nanscience and Nanotechnology 14 (2014) 7545-7552).But this method for coating needs reheating processing procedure, sternly It has impact on again with heat-flash sensitiveness inner nuclear material Li2CoPO4F structural stability.
At present, to fluorophosphoric acid cobalt lithium (Li2CoPO4F) research of high-voltage anode material is less, and most researchers are endeavoured It is modified in using single scheme, single modification scheme is making up Li2CoPO4F positive electrodes defect in a certain respect it is same When often bring other negative effects, such as Fe, Mn ion doping, reason is reduced while material intrinsic electric conductivity is improved By capacity.Further, since Li2CoPO4The heat sensitivity of F material structures, traditional cladding scheme secondary heat treatment easily cause Material structure destroys.Present invention selection, as doping object, is improving body with Ni elements similar in Co elements radius and energy level While material conductivity, not only without reversible discharge capacity is reduced, the available capacity of high voltage region is added on the contrary；In addition, Using in-stiu coating of the appropriate carbon in material preparation process, the structural stability of inner nuclear material is not influenceed, is effectively increased Intergranular electronic conductivity；Meanwhile utilize dielectric SiO2Targeting is optionally modified in Li2CoPO4F material granules At the border of particle, it can not only suppress microcell of the electrolyte at border and side reaction occurs, improve material structure stability, And SiO2The ionic adsorption characteristic of particle surface has effectively facilitated Li+In intergranular diffusion transport, advantage is formed with carbon coating Complementary synergy, the ionic conductivity and electron conduction of material are improved comprehensively, show it excellent forthright again Energy.And the SiO being related in the present invention2Cladding process does not carry out secondary high-temperature heat treatment to inner nuclear material, will not cause to tie Structure destroys.Metal ion (Ni) doping, carbon coating and oxide are coated three kinds of method of modifying combinations pair by the present invention first Material carries out modified synergic, realizes being obviously improved comprehensively for material electrochemical performance.
The content of the invention
The purpose of the present invention, the shortcomings of being to overcome the low electronics of positive electrode, ionic conductivity and poor circulation, adopt The fluorophosphoric acid cobalt lithium anode material of nickel doping and carbon/coated with silica modified synergic is prepared with hydro-thermal method.Obtained material Grain is small, and purity is high, by doping and Ni elements similar in Co radiuses and energy level, can effectively improve its intrinsic conductivity, simultaneously Strengthen the capacity of high voltage region, in addition, appropriate carbon coating in situ improves the electronic conductivity between material granule, meanwhile, SiO2 Target selective modification can effectively blocking electrode material and electrolyte pernicious interaction, reduce electrolyte in kernel material Expect the generation of microcell side reaction at particle border, improve the stability of inner nuclear material.The present invention is that a kind of cost is low, technique is simple Singly, it is easily achieved the method for modifying with volume production, there is provided a kind of high-voltage anode material with good chemical property.
To achieve these goals, the present invention provides the fluorine phosphorus of a kind of nickel doping and carbon/coated with silica modified synergic Sour cobalt lithium anode material and preparation method thereof, the chemical formula of the material is Li2Co1-x Ni x PO4F/C+SiO2, wherein 0<x≤ 0.3, Its preparation method comprises the following steps：
（1）The lithium source of certain stoichiometric proportion, cobalt source, Fluorine source and nickel source compound are separately added into deionized water, stirred, will A certain amount of phosphate radical source compound adds above-mentioned solution, continues to stir, transfers them to the closed hydro-thermal reaction of autoclave Afterwards, room temperature is naturally cooled to, is taken out, dries, obtains presoma；
（2）By step（1）The presoma of gained and carbon-source cpd mixed grinding, under an argon atmosphere, two benches calcining, obtain carbon Coat nickel doping Li2CoPO4F（Li2Co1-x Ni x PO4F/C）Material；
（3）A certain amount of silica is weighed in beaker, ionized water is added, ultrasound, adds Li2Co1-x Ni x PO4F/C materials Expect, magnetic agitation for a period of time, is dried under certain temperature, grinding, obtains nickel doping and carbon/coated with silica modified synergic Fluorophosphoric acid cobalt lithium（Li2Co1-x Ni x PO4F/C+SiO2）Target powder.
Further, step（1）Described in one or more of the lithium source for lithium hydroxide, in lithium acetate；Described cobalt Source is the one or more in cobalt acetate, cobalt nitrate, cobaltous sulfate, cobalt chloride；Described Fluorine source is one in lithium fluoride, hydrofluoric acid Kind is several；Described nickel source is the one or more in nickel chloride, nickel acetate, nickel nitrate, nickel sulfate；Described phosphoric acid root For ammonium dihydrogen phosphate, diammonium hydrogen phosphate, the one or more in phosphoric acid.Step（2）Described in carbon source for glucose, sucrose, The carbon such as the organic matter such as citric acid, ascorbic acid, pyrroles, thiophene carbon source or graphite, graphene oxide, carbon nano-fiber, Ketjen black One or more in cellulosic material.
Further, step（1）Described in addition phosphate radical source compound after magnetic agitation time 5-30 min, it is closed Hydrothermal temperature is 120-220 DEG C, and the hydro-thermal time is 8-20 h.Step（2）Described in carbon-source cpd in addition be Weight/mass percentage composition of the carbon content in target product is 1-20 wt%；Step（2）Described in by step（1）The forerunner of gained Body mixes direct dry grinding or both for both with carbon-source cpd mixed grinding process and is put into water or ethanol equal solvent Solvent is evaporated off in scattered wet-mixing grinding again.
Further, step（2）Described in first stage calcining heat be 300-400 DEG C, calcination time is 4-7 h, Second stage calcining heat is 550-700 DEG C, and calcination time is 4-8 h；Processing mode is one between described two benches calcining Through being cooled to room temperature between the processing of cooking-pot type continuous warming or two benches, after taking out grinding, then heating carries out second stage heat again Processing.
Further, step（3）Described in silica be particle, powder or dispersion liquid in one or more；Two The dispersant of silica dispersion liquid is the one or more in methanol, ethanol, ethylene glycol, water；The pH of silica dispersions is 8.5-11.5.Step（3）Described in sonication treatment time 10-90 min, 20-80 DEG C of the temperature of magnetic agitation, magnetic agitation Time be 1-6 h.Step（3）Described in the weight/mass percentage composition of silica be 0.5-10 wt%.
The beneficial effects of the invention are as follows：
（1）In Li2CoPO4The incorporation of F intracells and transition metal Ni elements similar in Co radiuses and energy level, form solid solution, Lattice defect is caused, improves the intrinsic electric conductivity of material, and improve effective discharge capacity of high-voltage region；
（2）In Li2CoPO4F surface in situ coats appropriate carbon, does not influence the structural stability of inner nuclear material, improves The electronic conductivity of intergranular；SiO2Targeting is optionally modified at the border of inner nuclear material particle and particle, can not only be pressed down Side reaction occurs for microcell of the electrolyte processed at border, improves material structure stability, and SiO2The ionic adsorption on surface has Beneficial to Li+In intergranular diffusion transport, improve the multiplying power and cycle performance of material.In addition, SiO2Modification is not to kernel Material carries out secondary high-temperature heat treatment, structure will not be caused to destroy.Pass through carbon coating and SiO2It is mutual that selective modification forms advantage The synergy of benefit, the ionic conductivity and electron conduction of material are improved comprehensively, it is shown excellent high rate performance.
Modified synergic scheme of the present invention can improve the electron conduction and ionic conductivity of material, and can protection The structural stability of material, thus, the Li after modified synergic2Co1-x Ni x PO4F/C+SiO2Material shows high power capacity, height Energy density and excellent multiplying power property and cycle performance, the fully optimized electrochemistry combination property of material.The present invention wants The technology and equipment asked is simple, it is easy to accomplish industrialization, and cost is cheap, is had a wide range of applications in anode material of lithium battery Prospect.
Brief description of the drawings
Fig. 1 is Li prepared by the embodiment of the present invention 12Co1-x Ni x PO4F/C+SiO2The XRD spectrum of positive electrode.
Fig. 2 is Li prepared by the embodiment of the present invention 22Co1-x Ni x PO4F/C+SiO2The SEM figures of positive electrode.
Fig. 3 is Li prepared by the embodiment of the present invention 22Co1-x Ni x PO4F/C+SiO2The FTIR figures of positive electrode.
Fig. 4 is Li prepared by the embodiment of the present invention 32Co1-x Ni x PO4F/C+SiO2Positive electrode and comparative example 1 and comparative example 2 prepare the discharge curve comparison diagram first of material.
Fig. 5 is Li prepared by the embodiment of the present invention 32Co1-x Ni x PO4F/C+SiO2Positive electrode and comparative example 1 and comparative example 2 prepare the multiplying power of material and cycle performance curve comparison figure.
Embodiment
For the ease of understanding the present invention, below in conjunction with the accompanying drawings, specific embodiment and comparative example the present invention is made it is further detailed Thin description.Obviously, described embodiment is the section Example of the present invention, and not all embodiments.Based on this invention Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all Belong to protection scope of the present invention.
The fluorophosphoric acid cobalt lithium anode material of a kind of nickel doping proposed by the present invention and carbon/coated with silica modified synergic and Its preparation method, materials chemistry expression formula are：Li2Co1-x Ni x PO4F/ C+SiO2, wherein 0<x ≤ 0.3。
Comparative example 1
Solid phase method prepares Li2CoPO4F positive electrodes：
（1）By Li: Co:The ratio between amount of F materials is 1.02:1:1 weighs LiOH.H2O、Co(CH3COO)2 .4H2O、NH4H2PO4, The h of dry mixed ball milling 3, tabletting, under an argon atmosphere, 400 DEG C of h of pre-burning 10,800 DEG C of 10 h of calcining of continuous warming, in obtaining Between product LiCoPO4；
（2）LiCoPO obtained above is weighed in proportion4Powder and LiF enter in mortar, grinding, tabletting, under an argon atmosphere, 700 DEG C of 1.5 h of calcining, obtain Li2CoPO4F positive electrodes.As shown in Figure 4, under 0.1 C, the first discharge specific capacity of material is 91.5 mAh g-1。
Comparative example 2
Hydro-thermal method prepares Li2CoPO4F positive electrodes：
（1）By LiOH.H2O、Co(CH3COO)2 .4H2O, LiF presses Li: Co:The ratio between amount of F materials is 2.02:1:1 in deionization Stirred in water, by H3PO4, LiF press PO4 3-:The ratio between amount of F materials is 1:1 H3PO4Instill in above-mentioned solution, continue to stir 8 min are mixed, transfer them to autoclave, the h of hydro-thermal 11 at 200 DEG C, naturally cool to room temperature, are taken out, dries, obtains light powder Color presoma；
（2）Presoma is ground, tabletting, under an argon atmosphere, 300 DEG C of h of pre-burning 7, continuous warming obtains to 650 DEG C of 5 h of calcining Li2CoPO4F positive electrodes.By this positive electrode and lithium piece assembled battery, carry out constant current charge-discharge test, voltage range 2.0 ~ Between 5.3 V.As shown in Figure 4, under 0.1 C, the first discharge specific capacity of material is 98.5 mAh g-1.As shown in Figure 5, material Material first discharge specific capacity under 0.1,0.5,1.0,2.0,5.0 C different multiplyings is respectively 98.5,80.7,68.1,41.2, 30.8 mAh g-1.After 18 circle different multiplying circulations, the specific discharge capacity maintenance after 10 circulations under 0.1 C is turned again to In 88.4 mAh g-1, capability retention 89.7%.
Embodiment 1
（1）By LiOH.H2O、Co(CH3COO)2 .4H2O、Ni(CH3COO)2 .4H2O, LiF presses Li: Co: Ni:The amount of F materials it Than for 2.02:0.93:0.07:1 stirs in deionized water, by H3PO4, LiF press PO4 3-:The ratio between amount of F materials is 1:1 H3PO4Instill in above-mentioned solution, continue to stir 8 min, transfer them to autoclave, the h of hydro-thermal 11 at 200 DEG C is natural Room temperature is cooled to, is taken out, dries, obtains presoma；
（2）It is 95 that above-mentioned nickel is adulterated into carbon in presoma and Ketjen black/ascorbic acid according to mass ratio:After 5 mixing, dry method is ground Mill, tabletting, under an argon atmosphere, 350 DEG C of pre-burning 6h, cools with stove, takes out grinding, tabletting, 650 DEG C of 5 h of calcining, obtains Li2Co0.93Ni0.07PO4F/ C-materials；
（3）0.5 g SiO 2 powders are weighed in beaker, ionized water is added, 30 min of ultrasound, it is above-mentioned to add 1.0 g Li2Co0.93Ni0.07PO4F/C materials, the h of magnetic agitation 4 at 30 DEG C, 80 DEG C of dryings, grinding, obtain nickel doping and carbon/titanium dioxide Silicon coats fluorophosphoric acid cobalt lithium（Li2Co0.93Ni0.07PO4F/C+SiO2）Positive electrode.By this material of Fig. 1 and Li2CoPO4F standard drawings Spectrum contrast understands that nickel doping and carbon/coated with silica modification do not have the structure for changing bulk material, are not introduced into Ni yet And SiO2The diffraction maximum of related substances, material prepared by the method have higher purity.
Embodiment 2
（1）By LiOH.H2O、Co(NO3)2 .6H2O、Ni(NO3)2 .6H2O, LiF presses Li: Co: Ni:The ratio between amount of F materials is 2.02:0.93:0.07:1 stirs in deionized water, by NH4H2PO4, LiF press PO4 3-:The ratio between amount of F materials is 1:1 NH4H2PO4Add in above-mentioned solution, continue to stir 15 min, transfer them to autoclave, the h of hydro-thermal 15 at 180 DEG C, Room temperature is naturally cooled to, is taken out, dries, obtains presoma；
（2）It is 90 that above-mentioned nickel is adulterated into carbon in presoma and glucose/sucrose according to mass ratio:After 10 mixing, add appropriate Ethanol, wet-milling, 60 DEG C of dryings, grinding, tabletting, under an argon atmosphere, 400 DEG C of h of pre-burning 4, plunge the sample into quenching-in water, Grinding, tabletting, 700 DEG C of 4 h of calcining, obtain Li2Co0.93Ni0.07PO4F/ C-materials；
（3）Weigh the nano silicon dioxide dispersion of 1.0 g pH=8.5（30.2%）In beaker, ionized water, ultrasound 40 are added Min, add the above-mentioned Li of 1.0 g2Co0.93Ni0.07PO4F/C materials, the h of magnetic agitation 3 at 50 DEG C, 80 DEG C of dryings, grinding, obtain To nickel doping and carbon/coated with silica fluorophosphoric acid cobalt lithium（Li2Co0.93Ni0.07PO4F/C+SiO2）Positive electrode.From SEM figures As can be seen that silica dioxide granule is coated on bulk material surface, and more it is coated on material granule border and intersection.From Fig. 3 FTIR figures are as can be seen that in 586-630 cm-1With 800-1230 cm-1There is PO in place, the material of preparation4 3-Group Bending and stretching vibration peak, in 3448 cm-1Nearby show SiO2Adsorption OH-The stretching vibration peak of group.In 760- 870 cm-1There is Si-O absworption peak in place, in 2258 and 3851 cm-1There is Ni-O absworption peak in place.
Embodiment 3
（1）By LiCH3COO.2H2O、CoSO4 .7H2O、NiSO4 .6H2O, HF presses Li: Co: Ni:The ratio between amount of F materials is 2.02:0.93:0.07:1 stirs in deionized water, by NH4H2PO4, LiF press PO4 3-:The ratio between amount of F materials is 1:1 NH4H2PO4Add in above-mentioned solution, continue to stir 20 min, transfer them to autoclave, the h of hydro-thermal 20 at 120 DEG C, Room temperature is naturally cooled to, is taken out, dries, obtains presoma；
（2）It is 85 that above-mentioned nickel is adulterated into carbon in presoma and carbon nano-fiber/pyrroles according to mass ratio:After 15 mixing, dry method Grinding, tabletting, under an argon atmosphere, 300 DEG C of h of pre-burning 7,600 DEG C of 5 h of calcining of continuous warming, obtain Li2Co0.93Ni0.07PO4F/ C-material；
（3）1.0 g silica dioxide granules are weighed in beaker, ionized water is added, 90 min of ultrasound, it is above-mentioned to add 1.0 g Li2Co0.93Ni0.07PO4F/C materials, the h of magnetic agitation 4 at 60 DEG C, 80 DEG C of dryings, grinding, obtain nickel doping and carbon/titanium dioxide Silicon coats fluorophosphoric acid cobalt lithium（Li2Co0.93Ni0.07PO4F/C+SiO2）Positive electrode.By this positive electrode and lithium piece assembled battery, Constant current charge-discharge test is carried out, voltage range is between 2.0 ~ 5.3 V.As shown in Figure 4, under 0.1 C, the electric discharge first of material Specific capacity is 143.6 mAh g-1.As shown in Figure 5, material discharges first under 0.1,0.5,1.0,2.0,5.0 C different multiplyings Specific capacity is respectively 143.6,107.1,89.7,63.5,44.5 mAh g-1.After 18 circle different multiplying circulations, turn again to Specific discharge capacity maintains 132.1 mAh g after 10 circulations under 0.1 C-1, capability retention is up to 92.0%.
Embodiment 4
（1）By LiOH.H2O、CoCl2 .6H2O、NiCl2 .6H2O, HF presses Li: Co: Ni:The ratio between amount of F materials is 2.02: 0.80:0.20:1 stirs in deionized water, by H3PO4, LiF press PO4 3-:The ratio between amount of F materials is 1:1 H3PO4Add Enter in above-mentioned solution, continue to stir 5 min, transfer them to autoclave, the h of hydro-thermal 8 at 220 DEG C, naturally cool to room Temperature, take out, dry, obtain presoma；
（2）It is 99 that above-mentioned nickel is adulterated into carbon in presoma and Ketjen black/thiophene according to mass ratio:After 1 mixing, add appropriate Ethanol, wet-milling, 60 DEG C of dryings, grinding, tabletting, under an argon atmosphere, 300 DEG C of h of pre-burning 7, quenching-in water is plunged the sample into, is ground Mill, tabletting, 550 DEG C of 8 h of calcining, obtain Li2Co0.80Ni0.20PO4F/ C-materials；
（3）Weigh the nano silicon dioxide dispersion of 1.5 g pH=10（30.2%）In beaker, ionized water, ultrasound 30 are added Min, add the above-mentioned Li of 1.0 g2Co080Ni0.20PO4F/C materials, the h of magnetic agitation 4 at 30 DEG C, 80 DEG C of dryings, grinding, obtain To nickel doping and carbon/coated with silica fluorophosphoric acid cobalt lithium（Li2Co0.80Ni0.20PO4F/C+SiO2）Positive electrode.
Embodiment 5
（1）By LiCH3COO.2H2O、Co(CH3COO)2 .4H2O、Ni(CH3COO)2 .4H2O, LiF presses Li: Co: Ni:F materials The ratio between amount be 2.02:0.85:0.15:1 stirs in deionized water, by H3PO4, LiF press PO4 3-:The amount of F materials it Than for 1:1 H3PO4Instill in above-mentioned solution, continue to stir 15 min, transfer them to autoclave, hydro-thermal 12 at 180 DEG C H, room temperature is naturally cooled to, taken out, dried, obtain presoma；
（2）It is 80 that above-mentioned nickel is adulterated into carbon in presoma and graphene oxide according to mass ratio:After 20 mixing, dry grinding, Tabletting, under an argon atmosphere, 350 DEG C of 6 h of calcining, cool with stove, take out grinding, tabletting, 650 DEG C of 6 h of calcining, obtain Li2Co0.85Ni0.15PO4F/ C-materials；
（3）Weigh the silica dispersions of 1.0 g pH=11.5（30.2%）In beaker, addition ionized water, 10 min of ultrasound, Add the above-mentioned Li of 1.0 g2Co0.85Ni0.15PO4F/C materials, the h of magnetic agitation 3 at 45 DEG C, 80 DEG C of dryings, grinding, obtain nickel Doping and carbon/coated with silica fluorophosphoric acid cobalt lithium（Li2Co0.85Ni0.15PO4F/C+SiO2）Positive electrode.

Claims (9)

1. a kind of nickel doping and the fluorophosphoric acid cobalt lithium anode material of carbon/coated with silica modified synergic, it is characterised in that：Fluorine phosphorus The formula of sour cobalt lithium anode material is Li2Co1-x Ni x PO4F/C+SiO2, wherein 0<x≤0.3。
2. a kind of preparation method of the fluorophosphoric acid cobalt lithium anode material of nickel doping and carbon/coated with silica modified synergic, it is special Sign is to comprise the following steps：（1）The lithium source of certain stoichiometric proportion, cobalt source, Fluorine source and nickel source compound are separately added into In ionized water, stirring, a certain amount of phosphate radical source compound is added into above-mentioned solution, continues to stir, it is anti-to transfer them to high pressure After answering the closed hydro-thermal reaction of kettle, room temperature is naturally cooled to, is taken out, dries, obtains presoma；（2）By step（1）The presoma of gained With carbon-source cpd mixed grinding, under an argon atmosphere, two benches calcining, carbon-coating nickel doping Li is obtained2CoPO4F（Li2Co1- x Ni x PO4F/C）Material；（3）A certain amount of silica is weighed in beaker, ionized water is added, ultrasound, adds Li2Co1- x Ni x PO4F/C materials, magnetic agitation for a period of time, is dried under certain temperature, grinding, obtains nickel doping and carbon/silica bag Cover the fluorophosphoric acid cobalt lithium of modified synergic（Li2Co1-x Ni x PO4F/C+SiO2）Target powder.
3. preparation method as claimed in claim 2, it is characterised in that step（1）Described in lithium source for lithium hydroxide, lithium acetate In one or more；Described cobalt source is the one or more in cobalt acetate, cobalt nitrate, cobaltous sulfate, cobalt chloride；Described fluorine Source is the one or more in lithium fluoride, hydrofluoric acid；Described nickel source is one in nickel chloride, nickel acetate, nickel nitrate, nickel sulfate Kind is several；Described phosphoric acid root is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, the one or more in phosphoric acid；
Step（2）Described in carbon source for the organic matter carbon source such as glucose, sucrose, citric acid, ascorbic acid, pyrroles, thiophene or One or more in the carbon materialses such as graphite, graphene oxide, carbon nano-fiber, Ketjen black.
4. preparation method as claimed in claim 2, it is characterised in that step（1）Described in addition phosphate radical source compound after magnetic Power mixing time 5-30 min, closed hydrothermal temperature are 120-220 DEG C, and the hydro-thermal time is 8-20 h.
5. preparation method as claimed in claim 2, it is characterised in that step（2）Described in carbon-source cpd in addition be carbon Weight/mass percentage composition of the content in target product is 1-20 wt%；Step（2）Described in by step（1）The presoma of gained Mix direct dry grinding or both for both with carbon-source cpd mixed grinding process and be put into water or ethanol equal solvent and divide Dissipate wet-mixing grinding and solvent is evaporated off again.
6. preparation method as claimed in claim 2, it is characterised in that step（2）Described in first stage calcining heat be 300- 400 DEG C, calcination time is 4-7 h, and second stage calcining heat is 550-700 DEG C, and calcination time is 4-8 h；Two described ranks Between section calcining processing mode be a cooking-pot type continuous warming handle or two benches between through being cooled to room temperature, after taking out grinding, then Again heating carries out second stage heat treatment.
7. preparation method as claimed in claim 2, it is characterised in that step（3）Described in silica for particle, powder or One or more in dispersion liquid；The dispersant of silica dispersions is methanol, ethanol, ethylene glycol, one kind in water or several Kind；The pH of silica dispersions is 8.5-11.5.
8. preparation method as claimed in claim 2, it is characterised in that step（3）Described in sonication treatment time 10-90 min, 20-80 DEG C of the temperature of magnetic agitation, the time of magnetic agitation is 1-6 h.
9. preparation method as claimed in claim 2, it is characterised in that step（3）Described in silica weight/mass percentage composition For 0.5-10 wt%.
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CN109830664A (en) * 2019-02-11 2019-05-31 长沙理工大学 A kind of original position double-layer carbon covered composite yarn electrode material and its preparation method and application
CN111137871A (en) * 2020-01-07 2020-05-12 济南大学 Tin antimony oxide coated lithium cobalt fluorophosphate and surface deposition in-situ coating method and application thereof
CN113716624A (en) * 2021-08-31 2021-11-30 蜂巢能源科技有限公司 Composite material, preparation method thereof and lithium ion battery anode material
CN114512644A (en) * 2020-11-17 2022-05-17 松山湖材料实验室 Positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery
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CN114933336A (en) * 2022-06-21 2022-08-23 宜宾锂宝新材料有限公司 Fluorine-phosphorus chaperone doped ternary precursor, preparation method thereof and ternary material

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CN109830664A (en) * 2019-02-11 2019-05-31 长沙理工大学 A kind of original position double-layer carbon covered composite yarn electrode material and its preparation method and application
CN111137871A (en) * 2020-01-07 2020-05-12 济南大学 Tin antimony oxide coated lithium cobalt fluorophosphate and surface deposition in-situ coating method and application thereof
CN111137871B (en) * 2020-01-07 2022-06-21 济南大学 Tin antimony oxide coated lithium cobalt fluorophosphate and surface deposition in-situ coating method and application thereof
CN114512644A (en) * 2020-11-17 2022-05-17 松山湖材料实验室 Positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery
CN114512644B (en) * 2020-11-17 2023-10-20 松山湖材料实验室 Positive electrode active material, preparation method thereof, positive electrode and lithium ion secondary battery
CN113716624A (en) * 2021-08-31 2021-11-30 蜂巢能源科技有限公司 Composite material, preparation method thereof and lithium ion battery anode material
CN114538535A (en) * 2022-01-28 2022-05-27 厦门厦钨新能源材料股份有限公司 Positive electrode material, precursor, preparation method of precursor and lithium ion battery
CN114538535B (en) * 2022-01-28 2023-12-15 厦门厦钨新能源材料股份有限公司 Positive electrode material, precursor, preparation method of precursor and lithium ion battery
CN114933336A (en) * 2022-06-21 2022-08-23 宜宾锂宝新材料有限公司 Fluorine-phosphorus chaperone doped ternary precursor, preparation method thereof and ternary material
CN114933336B (en) * 2022-06-21 2023-06-23 宜宾锂宝新材料有限公司 Fluorine-phosphorus chaperone doped ternary precursor, preparation method thereof and ternary material

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