CN106784809A - A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method - Google Patents

A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method Download PDF

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CN106784809A
CN106784809A CN201611015604.9A CN201611015604A CN106784809A CN 106784809 A CN106784809 A CN 106784809A CN 201611015604 A CN201611015604 A CN 201611015604A CN 106784809 A CN106784809 A CN 106784809A
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limpo
livopo
core
presoma
shell structure
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CN106784809B (en
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李涛
李航
周会
张敬捧
关成善
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Shandong Goldencell Electronics Technology Co Ltd
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    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method, i.e., first in positive electrode LiVOPO4Surface coating LiMPO4, C layers is then coated again, form LiVOPO4/LiMPO4/ C composite material of core-shell structure.Preparation method：By the LiVOPO of mass fraction 71 ~ 93%4Presoma, 5% ~ 20%LiMPO4Presoma is calcined 1 ~ 10h at 400 ~ 700 DEG C, can obtain a certain amount of LiMPO4The LiVOPO4 materials of cladding, add 2% ~ 9% carbon source, 2 ~ 10h is sintered under 500 ~ 800 DEG C of argon atmospheres and can be prepared by LiVOPO4/LiMPO4The complex lithium electric material of/C core shell structures.The present invention is by LiVOPO4Surface coating LiMPO4, C layers, form the composite of core shell structure, on the one hand Charge-transfer resistance can effectively be reduced, on the other hand the directly contact of electrolyte solution and electrode material can be reduced, the generation of side reaction between electrolyte solution and electrode material is avoided, so as to significantly improve the high rate performance and cycle performance of material.Product of the present invention can be used in as the lithium ion secondary battery anode material used in portable electric appts, electric automobile.

Description

A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method
Technical field
The invention belongs to electrode material preparing technical field, it is related to a kind of LiVOPO4/LiMPO4/ C core shell structure composite woods Material and preparation method.
Background technology
LiVOPO4Theoretical capacity reach 159mAh/g, Stability Analysis of Structures, discharge voltage and other positive active material phases When（It is 3.8-3.9V relative to lithium metal）, capacity can be fully used.Meanwhile, the resource of vanadium is enriched very much, China's vanadium Yield ranking third place in the world, and the price of vanadium is also more much lower than cobalt, considers from material cost, in China's research and development Li-V systems positive electrode compares LiCoO2Positive electrode has more and is of practical significance.LiVOPO4These advantages become One potential replacer of LiCoO2.
Literature research shows, LiVOPO4The maximum bottleneck that lithium ion battery is applied to as positive electrode is LiVOPO4 Electronic conductivity is low and lithium ion diffusion coefficient is slow wherein, cause its cycle performance undesirable.By conventional art Merely by LiVOPO4Mix with conductive auxiliary agent, it is difficult to solve this problem, although patent CN103346320A is proposed LiFePO4Coating modification, but LiFePO4Electronic conductivity itself is very low, and ionic diffusion coefficient is low, therefore improves smaller, and And mechanical mixture is used, material fusion effect is poor, has little effect.
So far, do not find by preparing LiVOPO4/LiMPO4/ C composite material of core-shell structure improves LiVOPO4 Multiplying power cryogenic property and cycle life research report.
The content of the invention
It is an object of the invention to be directed to LiVOPO4Electronic conductivity is low and lithium ion diffusion coefficient is slow wherein, lead Cause its cycle performance and the undesirable problem of high rate performance, there is provided one kind is using LiVOPO4 presomas, LiMPO4Presoma, carbon Source is obtained LiVOPO4/LiMPO4/ C composite material of core-shell structure, first in positive electrode LiVOPO4Surface coating LiMPO4, so Coat C layers again afterwards, form LiVOPO4/LiMPO4/ C composite material of core-shell structure.
Another object of the present invention is to provide above-mentioned LiVOPO4/LiMPO4The preparation side of/C composite material of core-shell structure Method.
Technical solution of the present invention is as follows：
A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure, with LiVOPO4It is kernel, kernel outer cladding LiMPO4Layer, table Face coats C layers again, and described composite particle diameter is 500~1000nm；Wherein LiVOPO4200~400nm of size of cores, LiMPO4Layer is 200~300nm, and C thickness degree is 100~300nm；
Described LiMPO4, M=（AxB1-x）, A be Mn, Co and Ni in one or several, B be Mg, Al, Ti, Zr and Cu in One or several, wherein 0<x<1.
Described LiVOPO4/LiMPO4/ C composite material of core-shell structure, is prepared from by the raw material of following mass percent： LiVOPO4Presoma 71~93%, LiMPO4Presoma 5%~20%, carbon source 2~9% amounts to 100%.
Described LiVOPO4 presomas and LiMPO4 presomas drops method, sol-gal process, solid phase method or micro- by chemical coprecipitation Wave heating method synthesizes；
Described carbon source is organic carbon source, preferably glucose and cellulose.
Above-mentioned LiVOPO4/LiMPO4The preparation method of/C composite material of core-shell structure, comprises the following steps：
(1) LiVOPO is prepared4Presoma and LiMPO4Presoma；
(2) by step（1）The LiVOPO of preparation4Presoma and LiMPO4Presoma is well mixed, and is calcined at 400~700 DEG C 1~10h, is obtained LiVOPO4/LiMPO4Composite；
(3) by step（2）Obtained LiVOPO4/LiMPO4 composites mix with carbon source, 500~800 DEG C of argon atmospheres 2~10h of lower sintering, obtains LiVOPO4/LiMPO4/ C composite material of core-shell structure.
Further, step（1）Described LiVOPO4Forerunner's preparation is preferably：Weigh etc. the amount of material point Analyse pure LiOH.H2O、NH4VO3、H3PO4And citric acid, respectively by LiOH.H2O、NH4VO3It is dissolved in 30~40 DEG C of water with citric acid The aqueous solution is obtained, then by above-mentioned each aqueous solution and H3PO4Mixing, mixed solution is placed on 70~80 DEG C of constent temperature heaters, obtains Gel, is placed in gel sample 90~105 DEG C of vacuum drying chambers and dries 8~10h, and fine grinding obtains LiVOPO4Presoma.
Further, step（1）Described LiMPO4Forerunner's preparation is preferably：Weigh 1：a：b：1：1 analysis Pure LiOHH2O, ASO4·7H2O、BSO4·7H2O、H3PO4And citric acid, wherein a+b=1, then by LiOH H2O、ASO4· 7H2O、BSO4·7H2O and citric acid are dissolved in 30~40 DEG C of water and obtain the aqueous solution respectively, then by above-mentioned each aqueous solution and H3PO4 Mixing, mixed solution is placed on 70~80 DEG C of constent temperature heaters, obtains gel, and gel sample is placed in into 90~105 DEG C of vacuum does Dry case dries 8~10h, and fine grinding obtains LiMPO4Presoma.
The above-mentioned LiVOPO of the present invention4/LiMPO4/ C composite material of core-shell structure can be applied to lithium electricity positive electrode, specifically may be used As the lithium ion secondary battery anode material used in portable electric appts, electric automobile.
Olivine-type lithium-containing transition metal doping phosphoric acid salt LiMPO4, wherein M=（AxB1-x）, A is transition metal, and B is The element of performance is improved, has the advantages that Stability Analysis of Structures, heat endurance are good, safe, and theoretical capacity is up to 170mAh g-1, it is current optimal anode material for lithium-ion batteries, and with electronic conductivity and ionic diffusion coefficient high, cladding In LiVOPO4On, then the good C of electric conductivity is coated, form the core shell structure LiVOPO with large current discharging capability4/ LiMPO4/ C composite.And corrosion of the electrolyte to internal layer positive electrode is prevented, side reaction is slow down, makes positive electrode Tend towards stability, increase cycle life；And electronic structure can optimize electronic structure with hydridization between nucleocapsid, with complex effect, LiVOPO can greatly be improved4High rate performance and cycle life.
Technical solution of the present invention has the beneficial effect that：
The present invention is by LiVOPO4Surface coating LiMPO4, C layers, form the composite of core shell structure, on the one hand can be with Charge-transfer resistance is effectively reduced, the directly contact of electrolyte solution and electrode material on the other hand can be reduced, it is to avoid electrolysis The generation of side reaction between matter solution and electrode material, so as to significantly improve the high rate performance and cycle performance of material.The present invention Product can be used in as the lithium ion secondary battery anode material used in portable electric appts, electric automobile.
Brief description of the drawings
Fig. 1 is LiVOPO prepared by embodiment 14/LiMPO4/ C composite material of core-shell structure electron-microscope scanning figures.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
Embodiment 1
A kind of LiVOPO4/LiMPO4The preparation method of/C composite material of core-shell structure, comprises the following steps：
(1) LiVOPO is prepared4Presoma and LiMPO4Presoma：
The pure LiOH of analysis of the amount of material such as weigh.H2O、NH4VO3、H3PO4And citric acid, respectively by LiOH.H2O、NH4VO3With Citric acid obtains the aqueous solution in being dissolved in 30~40 DEG C of water, then by each aqueous solution and H3PO4Mixing, mixed solution is placed in 80 DEG C of perseverances On warm heater, gel is obtained, gel sample is placed in into 105 DEG C of vacuum drying chambers dries 10h, after fine grinding, obtains LiVOPO4 Presoma.
Weigh 1：0.5：0.5：1：1 analysis pure LiOHH2O, MnSO4·7H2O、ZrSO4·7H2O、H3PO4And lemon Acid, and by LiOH H2O、MnSO4·7H2O、ZrSO4·7H2O and citric acid are dissolved in 30~40 DEG C of water respectively, then by each water Solution and H3PO4Mixing, mixed solution is placed on 80 DEG C of constent temperature heaters, obtains gel, and gel sample is placed in into 105 DEG C of vacuum Drying box dries 10h, after fine grinding, obtains Li (Mn0.5Zr0.5)PO4Presoma.
(2) by step（1）The LiVOPO of preparation4Presoma and LiMPO4Presoma is well mixed, and is calcined at 400 DEG C 1h, is obtained LiVOPO4/LiMPO4Composite；
(3) by step（2）Obtained LiVOPO4/LiMPO4Composite mixes with carbon source, is burnt under 500 DEG C of argon atmospheres Knot 2h, obtains LiVOPO4/LiMPO4/ C composite material of core-shell structure.
The material quality fraction set of embodiment 1 turns into：LiVOPO4Presoma 71%, LiMPO4Presoma 20%, glucose 9%.Institute The LiMPO for stating4, M=（AxB1-x）, A is Mn, and B is Zr, and x is 0.5.
A kind of LiVOPO obtained in embodiment 14/LiMPO4/ C composite material of core-shell structure（See Fig. 1）, with LiVOPO4For interior Core, kernel outer cladding LiMPO4Layer, surface coats C layers again, and described composite particle diameter is 1000nm；Wherein LiVOPO4Kernel Size 400nm, LiMPO4Layer is 300nm, and C thickness degree is 300nm.
LiVOPO obtained in embodiment 14/LiMPO4The chemical property of/C composite material of core-shell structure is surveyed as follows It is fixed：By sample, 3% carbon black SP, 2% graphite KS-15 and 5% Kynoar that mass fraction is 95%（PVDF), it is and molten Solution is in solvent N-methyl pyrilidone（NMP slurry is formed in), slurry is evenly coated on aluminium foil, the thickness of coating is about 110 μm.The electrode slice that will be coated is cut into the working electrode that area is 1cm2.48h is vacuum dried at 80 DEG C standby.Test electricity Pond, using conventional button cell, is to electrode, 1.0molL with metallic lithium foil-1 LiPF6Ethyl carbonate EC/ carbonic acid two Methyl esters（DMC）(volume ratio is 1：1）Solution is electrolyte, is assembled in the glove box full of argon gas, and digestion time is 12h.By 20mA/g（In terms of positive pole, equivalent to 0.1C）Speed charge to 4.2V, be discharged to 2.75V, discharge curve is obtained first To the discharge voltage plateau of the stabilization of 3.85V, reversible specific capacity is about 145mAh/g first, the capacity after being circulated through 150 times Conservation rate reaches 95.2%.And the capability retention of lower 80 circulations of 6.0C multiplying powers reaches 89%, -10 DEG C of capability retentions of low temperature are The 70% of 25 DEG C.
Embodiment 2
A kind of LiVOPO4/LiMPO4The preparation method of/C composite material of core-shell structure, comprises the following steps：
(1) LiVOPO is prepared4Presoma and LiMPO4Presoma：
The pure LiOH of analysis of the amount of material such as weigh.H2O、NH4VO3、H3PO4And citric acid, respectively by LiOH.H2O、NH4VO3With Citric acid is dissolved in 30~40 DEG C of water and obtains the aqueous solution, then by each aqueous solution and H3PO4Mixing, mixed solution is placed in 70 DEG C of constant temperature On heater, gel is obtained, gel sample is placed in into 95 DEG C of vacuum drying chambers dries 8h, after fine grinding, obtains LiVOPO4Forerunner Body.
Weigh 1：0.9：0.1：1：1 analysis pure LiOHH2O, MnSO4·7H2O、MgSO4·7H2O、H3PO4And lemon Acid, and by LiOH H2O、MnSO4•7H2O、MgSO4·7H2O and citric acid are dissolved in 30~40 DEG C of water respectively, then will be each water-soluble Liquid and H3PO4Mixing, mixed solution is placed on 80 DEG C of constent temperature heaters, obtains gel, and gel sample is placed in into 105 DEG C of vacuum does Dry case dries 10h, after fine grinding, obtains Li（Mn0.9Mg0.1）PO4Presoma.
(2) by step（1）The LiVOPO of preparation4Presoma and LiMPO4Presoma is well mixed, and is calcined at 550 DEG C 6h, is obtained LiVOPO4/LiMPO4Composite；
(3) by step（2）Obtained LiVOPO4/LiMPO4Composite mixes with carbon source, is burnt under 650 DEG C of argon atmospheres Knot 5h, obtains LiVOPO4/LiMPO4/ C composite material of core-shell structure.
The material quality fraction set of embodiment 1 turns into：LiVOPO4Presoma 80%, LiMPO4 presomas 13%, cellulose 7%. Described LiMPO4, M=（AxB1-x）, A is Mn, and B is Mg, and x is 0.9.
A kind of LiVOPO obtained in embodiment 24/LiMPO4/ C composite material of core-shell structure, with LiVOPO4It is kernel, kernel Outer cladding LiMPO4Layer, surface coats C layers again, and described composite particle diameter is 800nm；Wherein LiVOPO4Size of cores 300nm, LiMPO4Layer is 200nm, and C thickness degree is 300nm.
By LiVOPO obtained in embodiment 2 that mass fraction is 95%4/LiMPO4/ C composite material of core-shell structure sample, 3% Carbon black SP, 2% graphite KS-15 and 5% Kynoar（PVDF), it is made electrode slice by the method for embodiment 1 and is assembled into electricity Pond.By 20mA/g（In terms of positive pole, equivalent to 0.1C）Speed charge to 4.2V, be discharged to 2.75V, discharge curve is obtained first The discharge voltage plateau of the stabilization of 3.85V, first reversible specific capacity be about 148mAh/g, through 150 times circulate after capacity protect Holdup reaches 97.2%.And the capability retention of lower 80 circulations of 6.0C multiplying powers reaches 90%, -10 DEG C of capability retentions of low temperature are The 76% of 25 DEG C.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.

Claims (10)

1. a kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure, it is characterised in that：With LiVOPO4It is kernel, kernel outsourcing Cover LiMPO4Layer, surface coats C layers again, and described composite particle diameter is 500~1000nm；Wherein LiVOPO4Size of cores 200~400nm, LiMPO4Layer is 200~300nm, and C thickness degree is 100~300nm；
Described LiMPO4, M=（AxB1-x）, A be Mn, Co and Ni in one or several, B be Mg, Al, Ti, Zr and Cu in One or several, wherein 0<x<1.
2. LiVOPO according to claim 14/LiMPO4/ C composite material of core-shell structure, it is characterised in that：By following matter The raw material for measuring percentage is prepared from：LiVOPO4Presoma 71~93%, LiMPO4Presoma 5%~20%, carbon source 2~9%, always Meter 100%.
3. LiVOPO according to claim 24/LiMPO4/ C composite material of core-shell structure, it is characterised in that：Described LiVOPO4Presoma and LiMPO4Presoma drops method, sol-gal process, solid phase method or microwave heating method and synthesizes by chemical coprecipitation.
4. LiVOPO according to claim 24/LiMPO4/ C composite material of core-shell structure, it is characterised in that：Described carbon Source is organic carbon source.
5. LiVOPO according to claim 44/LiMPO4/ C composite material of core-shell structure, it is characterised in that：Described has Machine carbon source is glucose or cellulose.
6. the LiVOPO described in a kind of any one of claim 1-54/LiMPO4The preparation method of/C composite material of core-shell structure, its It is characterised by：Comprise the following steps：
(1) LiVOPO is prepared4Presoma and LiMPO4Presoma；
(2) by step（1）The LiVOPO of preparation4Presoma and LiMPO4Presoma is well mixed, and 1 is calcined at 400~700 DEG C ~10h, is obtained LiVOPO4/LiMPO4Composite；
(3) by step（2）Obtained LiVOPO4/LiMPO4 composites mix with carbon source, 500~800 DEG C of argon atmospheres 2~10h of lower sintering, obtains LiVOPO4/LiMPO4/ C composite material of core-shell structure.
7. preparation method according to claim 6, it is characterised in that step（1）Described LiVOPO4Presoma preparation side Method is：The pure LiOH of analysis of the amount of material such as weigh.H2O、NH4VO3、H3PO4And citric acid, respectively by LiOH.H2O、NH4VO3With Citric acid obtains the aqueous solution in being dissolved in 30~40 DEG C of water, then by above-mentioned each aqueous solution and H3PO4Mixing, mixed solution is placed in 70 On~80 DEG C of constent temperature heaters, gel is obtained, gel sample is placed in into 90~105 DEG C of vacuum drying chambers dries 8~10h, fine grinding, Obtain LiVOPO4Presoma.
8. preparation method according to claim 6, it is characterised in that step（1）Described LiMPO4Forerunner's preparation For：Weigh 1：a：b：1：1 analysis pure LiOHH2O, ASO4·7H2O、BSO4·7H2O、H3PO4And citric acid, wherein a+b= 1, then by LiOH H2O、ASO4·7H2O、BSO4·7H2O and citric acid obtain the aqueous solution in being dissolved in 30~40 DEG C of water respectively, Again by above-mentioned each aqueous solution and H3PO4Mixing, mixed solution is placed on 70~80 DEG C of constent temperature heaters, gel is obtained, by gel sample Product are placed in 90~105 DEG C of vacuum drying chambers and dry 8~10h, and fine grinding obtains LiMPO4Presoma.
9. LiVOPO according to claim 14/LiMPO4/ C composite material of core-shell structure, it is characterised in that：Can be applied to Lithium electricity positive electrode.
10. LiVOPO according to claim 94/LiMPO4/ C composite material of core-shell structure, it is characterised in that：Can be used as just Take the lithium ion secondary battery anode material used in formula electronic equipment, electric automobile.
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CN108574093A (en) * 2018-05-08 2018-09-25 浙江农林大学 A kind of carbon/Titanium pyrophosphate composite material and preparation method

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