A kind of high-performance composite materials and its preparation method and application
Technical field
The present invention relates to a kind of technical field of composite materials is and in particular to a kind of prepare high property using traditional bean jelly facture
Application in energy composite, preparation method and lithium ion battery.
Background technology
Lithium ion battery has that open-circuit voltage is high, energy density is big, long service life, memoryless effect, of low pollution and
The advantages of self-discharge rate is little, it is better than other traditional secondary batteries on overall performance, is considered as unanimously various portable electrics
Sub- equipment and ideal power supply used for electric vehicle.Although conventional lithium ion battery negative material graphite good cycling stability with
And cost performance is higher, but because its charging and discharging capacity is relatively low, volume and capacity ratio does not even more have advantage it is difficult to meet dynamical system
The system particularly electric motor car and hybrid electric vehicle requirement to cell high-capacity.Therefore exploitation has height ratio capacity, high charge-discharge
Efficiency, the great urgency of novel cathode material for lithium ion battery of long circulation life.
In the research of new non-carbon negative material, the pure metals such as silicon, tin, germanium, metal oxide and composition metal
Oxide material increasingly attracts attention because having higher theory embedding lithium capacity.If the negative material of these high power capacity can reach
Degree of being practical, will make the range of application of lithium ion battery significantly widen.But, the negative material of these high power capacity is mostly electric
Conductance is relatively low, and under the conditions of high level removal lithium embedded, there is serious bulk effect, causes the cyclical stability of electrode poor.
For the volume efficiency of the negative material of these high power capacity, it is combined with the carrier with elasticity and stable performance, buffers silicon
Volume Changes, the effective way improving its cyclical stability while high power capacity will be to maintain.In order to improve negative pole further
The performance of material, in addition to active material being carried out with cladding and processes, increasing by a sheaf space structure in composite is also very
It is necessary.Because the presence of this sheaf space structure can maintain the complete of electrode structure and stability further thus reducing electrode
Deformation, so as to improve the chemical property of combination electrode further.
Traditional bean jelly manufacture craft is simple, environmental protection, wide material sources, but it is ground using in field of composite material preparation
Study carefully fresh for rare.At present, in prior art, electrode material complicated process of preparation, the prices of raw materials are high, and the electricity prepared
Pole cyclical stability is poor, high rate performance is not excellent, and the feature of environmental protection is poor.
Content of the invention
Goal of the invention:High for electrode material complicated process of preparation, the prices of raw materials in prior art, and prepare
Electrode cycle stability is poor, the drawback such as high rate performance is not excellent, it is an object of the invention to provide a kind of cool using tradition
Powder facture prepares the application in high-performance composite materials, preparation method and lithium ion battery.
Technical scheme:In order to realize foregoing invention purpose, the invention discloses a kind of high-performance composite materials, described compound
Material is mainly made by water soluble starch and active material, and starch is deposited through high temperature cabonization, the nano particle of active material
It is the inside of carbon structure, form clad structure, in whole composite construction, there is abundant microcellular structure.
Described abundant microcellular structure refers to exist the micropore knot of uniform or non-homogeneous arrangement in whole composite construction
Structure, throughout whole material surface.
Preferably, described active material is nano silica fume, Ge powder, nanometer glass putty, nano-stannic oxide, nano oxygen
Change tungsten, nano zine oxide, nano indium oxide, nanometer zinc manganate, nanometer cobalt acid one or more of manganese and nanometer Manganese Ferrite.
As another kind preferably, described water soluble starch is commercially available peameal or mealy potato.
Present invention also offers the preparation method of described high-performance composite materials, comprise the following steps:
(1) batch mixing:By active material, conductive agent, pore creating material and water soluble starch, it is dividedly in some parts in deionized water, warp
Cross ultrasonic, stir process to be sufficiently mixed uniformly;
(2) high-temperature process:The mixture that step (1) is obtained is processed through high-temperature stirring, is allowed to solidify;
(3) freeze-drying:After the solidification composite that step (2) is obtained is via freezing processing, then through freeze-drying
Process, prepare dehydrating mixt;
(4) high temperature cabonization:Step (3) is obtained dehydrating mixt and prepares high-performance through high temperature cabonization sintering processes
Composite.
Preferably, described active material is directly to use, or using front through high temperature sintering process.
As another kind preferably, described conductive agent is carboxylation CNT or graphene oxide.
As another kind preferably, described pore creating material is EO20PO70EO20 (PEO-polycyclic for triblock copolymer
Ethylene Oxide-PEO triblock copolymer, abbreviation P123) or EO106PO70EO106 (PluronicF127, referred to as
F127) one kind therein.
As another kind preferably, the mass ratio of described pore creating material and active material is (20:1)~(1:2.5);Described conduction
The mass ratio of agent and active material is (0:1)~(0.5:1);The mass ratio of described water soluble starch and active material is (50:1)
~(2:1);The mass ratio of described deionized water and water soluble starch is (20:1)~(40:1).
As another kind preferably, described high temperature cabonization sintering condition is:Under inert atmosphere Ar gas, temperature is 500~900
DEG C it is sintered.
The present invention finally additionally provides application in preparing lithium battery for the described high-performance composite materials, by described composite wood
As li-ion electrode negative material after expecting to be fully ground, and carbon black and carboxymethylcellulose calcium are according to a certain percentage, mix,
It is vacuum dried after film, obtain final product lithium ion battery combination electrode.Employ the circulation of the composite negative pole of above-mentioned composite preparation
Performance and high rate performance can be greatly improved.
The present invention prepares high-performance composite materials using traditional bean jelly facture, is dissolved at high temperature using water soluble starch
In the characteristic of water, active material, pore creating material and conductive agent are sufficiently mixed with amidin in advance, in the event of high temperatures,
Active material fixed by bean jelly, then carries out processed by cryodesiccated method, via high temperature cabonization process preparation
Become.Gained composite includes containing abundant macropore and meso-hole structure, and these pore structures provide enough bufferings to active material
Space, can maintaining the complete of electrode structure and stability further, reducing the deformation of electrode, thus improving combination electrode further
Chemical property.
Beneficial effect:The invention provides a kind of high-performance containing abundant pore structure using traditional bean jelly facture preparation
Composite, and preparation method thereof and the application in lithium ion battery, compared with prior art there is advantages below:
(1) the chemical property improvement enriching the presence of pore structure and the uniform cladding of material with carbon element to active material is bright
Aobvious.
(2) present invention process step is simple, reproducible, high income, and the cheap wide material sources of the cost of raw material synthesized
Journey environmental protection, has preferable scale application potential.
(3) composite that the present invention provides is applied to prepare li-ion electrode as negative material, and cyclical stability is good
Good, charge-discharge performance is excellent.
Brief description
Fig. 1 is the digital camera photo and microphotograph before and after sample prepared by embodiment 1 sinters;
Fig. 2 is the SEM photograph after sample sintering prepared by embodiment 1;
TEM photo after sample sintering prepared by Fig. 3 embodiment 1;
Fig. 4 is for prepared electrode in embodiment 1 in 400mA g-1Charging and discharging currents density under cycle performance test bent
Line;
Specific embodiment
With reference to specific embodiment, the present invention is further described, and the description of specific embodiment is only substantially model
Example, following examples are implemented based on technical solution of the present invention, give detailed embodiment and specific operating process,
But protection scope of the present invention is not limited to following embodiments.
Embodiment 1
By the Si powder of 100nm in 500 DEG C of sintering 1h of Muffle furnace high temperature.The silica flour after 0.12g sintering is taken to be dispersed in 20mL
Ultrasonic in deionized water uniformly then by 0.2g P123,1g peameal is dispersed therein, and is stirred at room temperature uniformly, is then heated to
Pasty state, puts into freezing 6h in refrigerator.Then, freeze-drying, 600 degree of Ar gas sintering 3h prepare target combination electrode material.
As li-ion electrode negative material after composite after grinding is fully ground, and carbon black and carboxymethyl cellulose
Element, according to the ratio of parts by weight 70: 15: 15, mixes, and after film, 70 DEG C of vacuum drying 6h, prepare lithium ion battery
Combination electrode.This combination electrode is placed in 2025 battery cases, is to electrode with lithium piece, with polyethylene film as barrier film, with 1M
LiPF6+ EC/DEC (v/v=1/1) and containing a small amount of FEC additive be electrolyte assembled battery in 400mA g-1Discharge and recharge
Carry out constant current charge-discharge test under current density, test the cyclical stability that li-ion electrode prepared by this composite.
Can be seen that combination electrode from the digital camera photo before and after sample sintering prepared by Fig. 1 and microphotograph
Material remains substantial amounts of microcellular structure after sintering;As can be seen that Si nano particle is in composite wood from the SEM photograph of Fig. 2
The surface of material retains less;The TEM of Fig. 3 shows, Si nano particle is present in the inside of carbon structure substantially, defines good bag
Cover structure.Fig. 4 shows, with respect to the electrode of the Si material not being wrapped by, compound electrode cycle performance improvement is larger, 100
After circulation, discharge capacity is from 80mAh g-1Improve to 980mAh g-1.
Embodiment 2
By the Si powder of 100nm in 500 DEG C of sintering 1h of Muffle furnace high temperature.Take 0.01g graphene oxide to be dispersed in 40mL to go
It is ultrasonic in ionized water that uniformly then the silica flour after sintering 0.02g is dispersed in above-mentioned mixed solution, ultrasonic uniformly after by 0.4g
F127,1g peameal is dispersed therein, and is stirred at room temperature uniformly, is then heated to pasty state, puts into freezing 6h in refrigerator.Then, cold
Lyophilized dry, 900 degree of Ar gas sintering 2h prepare target combination electrode material.
Gained composite, through SEM and TEM detection, the structure basic simlarity with embodiment 1 resulting materials.
As li-ion electrode negative material after composite after grinding is fully ground, and carbon black and carboxymethyl cellulose
Element, according to the ratio of parts by weight 70: 15: 15, mixes, and after film, 70 DEG C of vacuum drying 6h, prepare lithium ion battery
Combination electrode.This combination electrode is placed in 2025 battery cases, is to electrode with lithium piece, with polyethylene film as barrier film, with 1M
LiPF6+ EC/DEC (v/v=1/1) and containing a small amount of FEC additive be electrolyte assembled battery in 400mA g-1Discharge and recharge
Carry out constant current charge-discharge test under current density, test this hollow titanium coated Si composite and prepare li-ion electrode
Cyclical stability.With respect to nano Si mosaic electrode, the electrode cycle performance improvement that the present invention is combined is larger, after 200 circulations
Discharge capacity is from 40mAh g-1Improve to 480mAh g-1.
Embodiment 3
By the Si powder of 100nm in 500 DEG C of sintering 1h of Muffle furnace high temperature.0.1g carboxylation multi-arm carbon nano-tube is taken to be dispersed in
It is ultrasonic in 30mL deionized water that uniformly then the silica flour after sintering 0.2g is dispersed in above-mentioned mixed solution, ultrasonic uniformly after will
0.2g P123,1g peameal is dispersed therein, and is stirred at room temperature uniformly, is then heated to pasty state, puts into freezing 6h in refrigerator.So
Afterwards, freeze-drying, 500 degree of Ar gas sintering 6h prepare target combination electrode material.
Gained composite, through SEM and TEM detection, the structure basic simlarity with embodiment 1 resulting materials.
As li-ion electrode negative material after composite after grinding is fully ground, and carbon black and carboxymethyl cellulose
Element, according to the ratio of parts by weight 70: 15: 15, mixes, and after film, 70 DEG C of vacuum drying 6h, prepare lithium ion battery
Combination electrode.This combination electrode is placed in 2025 battery cases, is to electrode with lithium piece, with polyethylene film as barrier film, with 1M
LiPF6+ EC/DEC (v/v=1/1) and containing a small amount of FEC additive be electrolyte assembled battery in 400mA g-1Discharge and recharge
Carry out constant current charge-discharge test under current density, test this hollow titanium coated Si composite and prepare li-ion electrode
Cyclical stability.With respect to the electrode of the Si material not being wrapped by, compound electrode cycle performance improvement is larger, 100 circulations
Discharge capacity is from 80mAh g afterwards-1Improve to 1160mAh g-1.
Embodiment 4
The Sn powder 0.5g of 100nm is dispersed in ultrasonic uniform in 30mL deionized water, then 0.2g F127 is dispersed in above-mentioned
In mixed solution, ultrasonic uniformly after 1g peameal is dispersed therein, be stirred at room temperature uniformly, be then heated to pasty state, put into ice
6h is freezed in case.Then, freeze-drying, 500 degree of Ar gas sintering 6h prepare target combination electrode material.
Gained composite, through SEM and TEM detection, the structure basic simlarity with embodiment 1 resulting materials.
As li-ion electrode negative material after composite after grinding is fully ground, and carbon black and carboxymethyl cellulose
Element, according to the ratio of parts by weight 70: 15: 15, mixes, and after film, 70 DEG C of vacuum drying 6h, prepare lithium ion battery
Combination electrode.This combination electrode is placed in 2025 battery cases, is to electrode with lithium piece, with polyethylene film as barrier film, with 1M
LiPF6+ EC/DEC (v/v=1/1) and containing a small amount of FEC additive be electrolyte assembled battery in 400mA g-1Discharge and recharge
Carry out constant current charge-discharge test under current density, test this hollow titanium coated Si composite and prepare li-ion electrode
Cyclical stability.With respect to the electrode of nanometer Sn particle, compound electrode cycle performance improvement is larger, discharges after 300 circulations
Capacity is from 240mAh g-1Improve to 980mAh g-1.
In sum, using the combination electrode material reactive nanoparticles of traditional bean jelly manufacture craft and associated materials preparation
Successfully it is coated in the material with carbon element of porous, abundant pore structure makes active material particle great in charge and discharge process
Volumetric expansion is effectively suppressed, thus greatly improving the cyclical stability that composite is used as li-ion electrode.
Preparing raw material of the present invention is cheap, and operating procedure is simple, high income, and the charge-discharge performance of material is excellent, is easy to industry
Metaplasia is produced.