CN107240680A - Hard carbon-metal oxide-soft carbon composite material and preparation method and application thereof - Google Patents
Hard carbon-metal oxide-soft carbon composite material and preparation method and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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Abstract
The invention discloses a hard carbon-metal oxide-soft carbon composite material and a preparation method and application thereof.A hard carbon precursor is prepared by a hydro-thermal method of a hydrocarbon in a reaction kettle, then the hard carbon precursor and titanium salt are pre-coated, and asphalt is placed in a muffle furnace for low-temperature pyrolysis reaction to obtain a soft carbon precursor; and finally, fully mixing the pre-coated hard carbon precursor and the soft carbon precursor, and carrying out high-temperature pyrolysis reaction under the protection of inert gas to obtain a product, namely a hard carbon-metal oxide-soft carbon composite material, wherein the material can be used as a negative electrode active material of a sodium ion battery. The raw materials used by the invention have wide sources and low cost; the prepared hard carbon-metal oxide-soft carbon composite material has the advantages of large reversible capacity, high first charge-discharge coulombic efficiency, good cycle performance and the like in a sodium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of composite, and in particular to a kind of hard carbon-metal oxide-soft carbon is combined
Material and its preparation method and application.
Background technology
Compared to secondary cells such as traditional lead-acid battery, nickel-cadmium cells, lithium ion battery has operating voltage height, energy
Density is big, have extended cycle life and advantages of environment protection, thus has attracted the concern of increasing scientific research personnel.But the whole world
Lithium resource is not rich, and elemental lithium is only 0.006% in crustal abundance, and resource turns into following large-scale application with price problem
Suffering, needs the exploitation energy-storage battery new system of future generation with excellent comprehensive effectiveness badly.Compared with lithium resource, sodium reserves are extremely rich
In richness, the earth's crust is about 2.64% containing degree, and the two is same major element, and chemical property is close, and lithium exploitation sodium is substituted with sodium
Ion battery has boundless application prospect.
The negative material generally used in current lithium ion battery is native graphite, Delanium etc., and it has excellent
It is difficult to be embedded into graphite layers away from for cycle performance, but the sodium ion of relatively large radius, thus the new sodium of exploitation
Ion battery cathode material has turned into the emphasis that people study.
Hard carbon is the pyrolytic carbon of high molecular polymer, and it is difficult to be graphitized, and it has interlaced layer structure, from
And sodium ion is embedded in and is deviate from from all angles, so as to substantially increase the speed of discharge and recharge；Compared with graphite material,
Its cryogenic property is obviously improved, and hard carbon material typically has higher reversible specific capacity, but hard carbon material
Often there is the shortcomings of electrode potential is too high, current potential is delayed, irreversible first, capacity is big, be restricted its large-scale application.
The agraphitic carbon that soft carbon material can be graphitized at a high temperature of referring to more than 2500 DEG C, is compared, it has with hard carbon material
Less specific surface area and preferable electrolyte compatibility.Compared with the carbon material applied at present, TiO2With dielectric constant it is high,
The performance such as chemical stability and good thermal stability, thus show in sodium-ion battery irreversible capacity loss first it is small,
Many advantages, such as having a safety feature.Therefore the present invention passes through pair of metal oxide and soft carbon material using hard carbon material as kernel
Layer cladding, prepares hard carbon-metal oxide-soft carbon composite, with lithium-ion electric of the composite as active material
Pond has the advantages that reversible capacity height, good cycle, security performance are high, while its preparation method is simple, it is with low cost.
The content of the invention
The present invention is intended to provide the anode material of lithium-ion battery of a kind of cheap, good cycle and high power capacity and
Its preparation method.
The present invention is realized by following scheme：
A kind of preparation method of hard carbon-metal oxide-soft carbon composite, it comprises the following steps：
1) the hydrocarbon aqueous solution is put into reactor and carries out hydro-thermal reaction, be subsequently washed with water to pH neutrality, do
It is dry to obtain hard carbon presoma；
2) hard carbon presoma and titanium salt are added and are stirred in the mixed solution of solvent and deionized water, treat that titanium salt is abundant
Dried after hydrolysis, obtain pre-coated hard carbon presoma；
3) pitch is placed in progress low temperature pyrogenation reaction in Muffle furnace, to decompose light component therein, obtains soft carbon forerunner
Body；
4) pre-coated hard carbon presoma and soft carbon presoma are well mixed, carried out under the protection of inert gas high
Warm pyrolytic reaction, obtains hard carbon-metal oxide-soft carbon composite.
Further scheme, the step 1) in hydrocarbon be in glucose, sucrose, lignin, cellulose at least
It is a kind of；The temperature of the hydro-thermal reaction is 100~300 DEG C.
Further scheme, the step 2) in titanium salt be butyl titanate or isopropyl titanate；The solvent is ethanol, second two
The volume ratio of one kind in alcohol, propane diols, the solvent and deionized water is 3:7, wherein solvent mainly plays dispersant.
Further scheme, the step 3) in pitch be in coal tar asphalt, mesophase pitch, asphalt at least
It is a kind of；The temperature of low temperature pyrogenation reaction is 25~400 DEG C, the time is 12~48h.
Hard carbon presoma, titanium salt and soft carbon in further scheme, the hard carbon-metal oxide-soft carbon composite
The mass ratio of presoma is (60-100)：(5-20)：(5-20).
Further scheme, the step 4) in inert gas be nitrogen, argon gas or helium.
Further scheme, the step 4) in high temperature pyrolysis reaction temperature be 700~1200 DEG C, the time be 2~6h.
Second goal of the invention of the present invention is to provide through hard carbon-metal oxide prepared by above-mentioned preparation method-soft
Carbon composite.
The 3rd goal of the invention of the present invention is to provide the application of hard carbon-metal oxide-soft carbon composite, described hard
Carbon-metal oxide-soft carbon composite is used for the negative active core-shell material of sodium ion secondary battery.
The present invention synthesizes hard carbon-metal oxide-soft carbon composite by thermal decomposition method, and its kernel is hard carbon material,
With higher specific capacity, and its interlamellar spacing is big compared with graphite, and diffusion velocity of the lithium ion in hard carbon material is very fast, it is thus possible to
Improve the cryogenic property and high rate performance of battery.The clad of composite is that metal oxide and soft carbon materials double-layer are coated,
Metal oxide clad can not only reduce the irreversible capacity first of hard carbon material, and the stability of its structure ensure that negative pole material
The security of material；Soft carbon material has less specific surface area and good electric conductivity, and on the one hand improve composite can
Inverse capacity, is on the other hand conducive to reacting the stable fine and close SEI films of generation with electrolyte, it is ensured that the preferable circulation of battery again
Performance and higher efficiency for charge-discharge.
The raw material sources that the present invention is used are extensively, with low cost；Hard carbon-metal oxide-soft carbon prepared by the present invention is multiple
Condensation material has the advantages such as reversible capacity big, first charge-discharge coulombic efficiency height, good cycle in sodium-ion battery.
Embodiment
In order to further appreciate that the content of the invention and feature of the present invention, following examples are enumerated, but these embodiments are not
Limit the full content of inventive concept.
Embodiment 1
1) it is placed in after concentration being added into reactor for 0.5M D/W in baking oven, control oven temperature is 180
DEG C, the hydro-thermal reaction time is 8h；
2) to step 1) obtained by reactant be washed with deionized, suction filtration 3 times, to pH in neutrality, 80~120 DEG C of dryings
>=24h, obtains hard carbon persursor material；
3) hard carbon presoma and the ester of metatitanic acid fourth four are added to ethanol-water solution (volume ratio of ethanol and deionized water is
3:7) stirring 4h in, the filtration drying after the ester of metatitanic acid fourth four is fully hydrolyzed obtains pre-coated hard carbon presoma；
4) will be equipped with the crucible of pitch, to be put into Muffle furnace at 220 DEG C pyrolysis be 22h, after light component in pitch is decomposed
To soft carbon presoma；
5) by step 3) and step 4) obtained by two kinds of precursor products be sufficiently mixed by planetary ball mill, wherein hard carbon
Presoma, titanium salt, soft carbon forerunner body mass ratio are 60:20:20, mixture is subjected to high temperature cabonization under the protection of inert gas
Reaction, carburizing temperature is 800 DEG C, and the reaction time is 4h, finally gives hard carbon-metal oxide-soft carbon composite.
Embodiment 2
1) it is placed in after concentration being added into reactor for 0.5M D/W in baking oven, control oven temperature is 100
DEG C, the hydro-thermal reaction time is 16h；
2) to step 1) obtained by reactant be washed with deionized, suction filtration 3 times, to pH in neutrality, 80~120 DEG C of dryings
>=24h, obtains hard carbon persursor material；
3) hard carbon presoma and isopropyl titanate are added to the Glycol Mixture (volume ratio of ethylene glycol and deionized water
For 3:7) stirring 4h in, the filtration drying after isopropyl titanate is fully hydrolyzed obtains pre-coated hard carbon presoma；
4) will be equipped with the crucible of pitch, to be put into Muffle furnace at 220 DEG C pyrolysis be 22h, after light component in pitch is decomposed
To soft carbon presoma；
5) by step 3) and step 4) obtained by two kinds of precursor products be sufficiently mixed by planetary ball mill, wherein hard carbon
Presoma, titanium salt, soft carbon forerunner body mass ratio are 60:20:20, mixture is subjected to high temperature cabonization under the protection of inert gas
Reaction, carburizing temperature is 900 DEG C, and the reaction time is 4h, finally gives hard carbon-metal oxide-soft carbon composite.
Embodiment 3
1) it is placed in after concentration being added into reactor for 0.6M aqueous sucrose solution in baking oven, controls oven temperature at 180 DEG C,
The hydro-thermal reaction time is 10h；
2) to step 1) obtained by reactant be washed with deionized, suction filtration 3 times, it is dry at 80~120 DEG C to pH in neutrality
Dry >=24h, obtains hard carbon persursor material；
3) hard carbon presoma and the ester of metatitanic acid fourth four are added to propane diols-aqueous solution (volume of propane diols and deionized water
Than for 3:7) stirring 4h in, the filtration drying after the ester of metatitanic acid fourth four is fully hydrolyzed obtains pre-coated hard carbon presoma；
4) will be equipped with the crucible of pitch, to be put into Muffle furnace at 220 DEG C pyrolysis be 22h, after light component in pitch is decomposed
To soft carbon presoma；
5) by step 3) and step 4) obtained by two kinds of precursor products be sufficiently mixed by planetary ball mill, wherein hard carbon
Presoma, titanium salt, soft carbon forerunner body mass ratio are 80:10:10, mixture is subjected to high temperature cabonization under the protection of inert gas
Reaction, carburizing temperature is 900 DEG C, and the reaction time is 4h, finally gives hard carbon-metal oxide-soft carbon composite.
Embodiment 4
1) it is placed in after concentration being added into reactor for the 0.4M lignin aqueous solution in baking oven, control oven temperature is 240
DEG C, the hydro-thermal reaction time is 10h；
2) to step 1) obtained by reactant be washed with deionized, suction filtration 3 times, to pH in neutrality, 80~120 DEG C of dryings
>=24h, obtains hard carbon persursor material；
3) hard carbon presoma and the ester of metatitanic acid fourth four are added to ethanol-water solution (volume ratio of ethanol and deionized water is
3:7) stirring 4h in, the filtration drying after the ester of metatitanic acid fourth four is fully hydrolyzed obtains pre-coated hard carbon presoma；
4) will be equipped with the crucible of pitch, to be put into Muffle furnace at 220 DEG C pyrolysis be 22h, after light component in pitch is decomposed
To soft carbon presoma；
5) by step 3) and step 4) obtained by two kinds of precursor products be sufficiently mixed by planetary ball mill, wherein hard carbon
Presoma, titanium salt, soft carbon forerunner body mass ratio are 80:10:10, mixture is subjected to high temperature cabonization under the protection of inert gas
Reaction, carburizing temperature is 900 DEG C, and the reaction time is 4h, finally gives hard carbon-metal oxide-soft carbon composite.
Embodiment 5
1) it is placed in after concentration being added into reactor for 0.6M cellulose aqueous solution in baking oven, control oven temperature is 200
DEG C, the hydro-thermal reaction time is 8h；
2) to step 1) obtained by reactant be washed with deionized, suction filtration 3 times, to pH in neutrality, 80~120 DEG C of dryings
>=24h, obtains hard carbon persursor material；
3) hard carbon presoma and the ester of metatitanic acid fourth four are added to ethanol-water solution (volume ratio of ethanol and deionized water is
3:7) stirring 4h in, the filtration drying after the ester of metatitanic acid fourth four is fully hydrolyzed obtains pre-coated hard carbon presoma；
4) will be equipped with the crucible of pitch, to be put into Muffle furnace at 380 DEG C pyrolysis be 12h, after light component in pitch is decomposed
To soft carbon presoma；
5) by step 3) and step 4) obtained by two kinds of precursor products be sufficiently mixed by planetary ball mill, wherein hard carbon
Presoma, titanium salt, soft carbon forerunner body mass ratio are 90:5:5, mixture is carried out under the protection of inert gas to high temperature cabonization anti-
Should, carburizing temperature is 1200 DEG C, and the reaction time is 4h, finally gives hard carbon-metal oxide-soft carbon composite.
Embodiment 6
1) it is placed in after concentration being added into reactor for 0.6M cellulose aqueous solution in baking oven, control oven temperature is 300
DEG C, the hydro-thermal reaction time is 6h；
2) to step 1) obtained by reactant be washed with deionized, suction filtration 3 times, to pH in neutrality, 80~120 DEG C of dryings
>=24h, obtains hard carbon persursor material；
3) by hard carbon presoma and isopropyl titanate be added to ethanol-water solution (volume ratio of ethanol and deionized water be 3:
7) stirring 4h in, the filtration drying after isopropyl titanate is fully hydrolyzed obtains pre-coated hard carbon presoma；
4) will be equipped with the crucible of pitch, to be put into Muffle furnace at 380 DEG C pyrolysis be 22h, after light component in pitch is decomposed
To soft carbon presoma；
5) by step 3) and step 4) obtained by two kinds of precursor products be sufficiently mixed by planetary ball mill, wherein hard carbon
Presoma, titanium salt, soft carbon forerunner body mass ratio are 90:5:5, mixture is carried out under the protection of inert gas to high temperature cabonization anti-
Should, carburizing temperature is 1200 DEG C, and the reaction time is 4h, finally gives hard carbon-metal oxide-soft carbon composite.
Comparative example 1
1) it is placed in after concentration being added into reactor for 0.5M D/W in baking oven, control oven temperature is 180
DEG C, the hydro-thermal reaction time is 8h；
2) to step 1) obtained by reactant be washed with deionized, suction filtration 3 times, to pH in neutrality, 80~120 DEG C of dryings
>=24h, obtains hard carbon persursor material；
3) will be equipped with the crucible of pitch, to be put into Muffle furnace at 220 DEG C pyrolysis be 22h, after light component in pitch is decomposed
To soft carbon presoma；
4) by step 2) and step 3) obtained by two kinds of precursor products be sufficiently mixed by planetary ball mill, wherein hard carbon
Presoma, soft carbon forerunner body mass ratio are 90:10, mixture is subjected to high temperature cabonization reaction, carbon under the protection of inert gas
It is 800 DEG C to change temperature, and the reaction time is 4h, finally gives hard carbon-soft carbon composite.
Comparative example 2
1) it is placed in after concentration being added into reactor for 0.5M D/W in baking oven, control oven temperature is 180
DEG C, the hydro-thermal reaction time is 8h；
2) by step 1) obtained by hard carbon precursor product high temperature cabonization reaction is carried out under the protection of inert gas, be carbonized
Temperature is 800 DEG C, and the reaction time is 4h, finally gives hard carbon material.
Using the material of above example 1-6 and comparative example 1-2 preparations as sodium-ion battery negative active core-shell material, and to it
Carry out normal temperature discharge and recharge and cycle performance test：Hard carbon material and conductive agent, binding agent in mass ratio 8:1:1 is mixed with pole
Piece, metallic sodium is as to electrode, and electrolyte is 1mol/L NaFP6/EC：DMC=1：1(w:W), barrier film used is PP
(Celgard 2400), assembles button cell in argon gas atmosphere glove box, and make-up electricity carries out charge-discharge test, voltage range
For 0.001-2.0V (vs.Na+/ Na), current density is 50mA g-1.Each battery performance test result (data as shown in table 1 below
As a result be take test 3 times after average).
Table 1：Performance test
Note：Circulating battery test temperature is 25 DEG C, and current density is 50mA/g constant current charge-discharges.
As can be seen from Table 1, the composite in the present invention is use up by metal oxide and soft carbon double-coating structure
Pipe reduces discharge capacity first, but improves the coulombic efficiency first and capability retention of composite；On the other hand, it is excessive
Metal oxide cladding may also cause the relatively low electrical conductivity of composite, so as to reduce the cycle performance of composite.I.e.
Ratio of the invention by regulating and controlling hard carbon presoma, titanium salt and soft carbon presoma, makes hard carbon-metal oxide-soft carbon of preparation
Composite can effectively improve the coulombic efficiency first and capability retention of battery.
And the unused titanium salt of the hard carbon persursor material that is prepared in comparative example 1 carries out pre-coated, so its coulombic efficiency first
It is poor with capability retention；The hard carbon material prepared in comparative example 2 because uncoated, therefore its first capacity it is higher but larger
Specific surface area but causes higher irreversible capacity first, so as to reduce coulombic efficiency first and poor stable circulation
Property.
The preferred embodiment of the foregoing detailed description present invention, for those skilled in the art, it is possible to understand that
These embodiments can be carried out with a variety of changes, modification on the basis of prior art or be denatured, all should be by claims institute
In the protection domain of determination.
Claims (9)
1. a kind of preparation method of hard carbon-metal oxide-soft carbon composite, it is characterised in that：Comprise the following steps：
1）The hydrocarbon aqueous solution is put into reactor and carries out hydro-thermal reaction, be subsequently washed with water it is neutral to pH, it is dry
To hard carbon presoma；
2）Hard carbon presoma and titanium salt are added and are stirred in the mixed solution of solvent and deionized water, treats that titanium salt is fully hydrolyzed
After dry, obtain pre-coated hard carbon presoma；
3）Pitch is placed in progress low temperature pyrogenation reaction in Muffle furnace, to decompose light component therein, soft carbon presoma is obtained；
4）Pre-coated hard carbon presoma and soft carbon presoma are well mixed, high warm is carried out under the protection of inert gas
Solution reaction, obtains hard carbon-metal oxide-soft carbon composite.
2. preparation method according to claim 1, it is characterised in that：The step 1）Middle hydrocarbon be glucose,
At least one of sucrose, lignin, cellulose；The temperature of the hydro-thermal reaction is 100~300 DEG C.
3. preparation method according to claim 1, it is characterised in that：The step 2）In titanium salt be butyl titanate or different
Titanium propanolate；The solvent is one kind in ethanol, propane diols, and the volume ratio of the solvent and deionized water is 3:7.
4. preparation method according to claim 1, it is characterised in that：The step 3）In pitch for coal tar asphalt,
At least one of mesophase pitch, asphalt；The temperature of low temperature pyrogenation reaction is 25~400 DEG C, the time be 12~
48h。
5. preparation method according to claim 1, it is characterised in that：Hard carbon-metal oxide-soft carbon the composite
In hard carbon presoma, the mass ratio of titanium salt and soft carbon presoma be（60-100）：（5-20）：（5-20）.
6. preparation method according to claim 1, it is characterised in that：The step 4）In inert gas be nitrogen, argon
Gas or helium.
7. preparation method according to claim 1, it is characterised in that：The step 4）In high temperature pyrolysis reaction temperature
It is 2~6h for 700~1200 DEG C, time.
8. hard carbon-metal oxide-soft carbon composite prepared by a kind of preparation method as claimed in claim 1.
9. the application of hard carbon-metal oxide-soft carbon composite as claimed in claim 8, it is characterised in that：It is described hard
Carbon-metal oxide-soft carbon composite is used for the negative active core-shell material of sodium ion secondary battery.
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| CN116675213A (en) * | 2023-05-30 | 2023-09-01 | 洛阳师范学院 | A kind of carbon material and its preparation method and application |
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| GB202007627D0 (en) * | 2020-05-21 | 2020-07-08 | Faradion Ltd | Carbon anode materials |
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