CN108807919A - A kind of preparation method of three-dimensional carbon skeleton - Google Patents
A kind of preparation method of three-dimensional carbon skeleton Download PDFInfo
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Abstract
The present invention is a kind of preparation method of three-dimensional carbon skeleton.This method mixed glucose, ferrous sulfate first then by mixture and sodium chloride ball milling, then use infrared tabletting machine, sodium chloride are washed away after sintering is carbonized, three-dimensional carbon skeleton is made.Electronics may be implemented by putting the conduction to three dimensions in the material that the present invention obtains, and can improve the intergranular electronic conduction ability of positive electrode and reduce the enhancing positive electrode chemical property in turn that polarizes.
Description
The application is a kind of original application " preparation method of iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite " (application number
201610841343X, on 09 23rd, 2016 applying date) divisional application.
Technical field
The present invention relates to anode material for lithium-ion batteries preparation field, in particular to a kind of iron manganese phosphate for lithium/three-dimensional carbon skeleton/
The preparation method of carbon composite.
Background technology
Since sony companies release commodity lithium ion battery for the first time since 1991, lithium ion battery is with its open-circuit voltage
It is high, have extended cycle life, energy density is high, self discharge is low, memory-less effect, it is environmentally friendly the advantages that be widely used in people's work
Make, the various aspects of study, life.In recent years, as the market demand of power battery and large-scale power energy storage device constantly increases
Add, occurs the power using lithium ion battery as carrier and accumulation power supply successively.
LiFePO4 is tentatively realized be commercialized at present with its cheap cost and higher specific capacity, remarkable safety
Using, the lithium manganese phosphate of olivine structural is belonged to LiFePO4, have identical specific capacity, higher work with LiFePO4
Voltage (4.IV, LiFePO4 3.4V), it is higher than energy (701Wh/Kg, LiFePO4 586Wh/Kg), it is less expensive
Cost, however compared to LiFePO4, lithium manganese phosphate intracell resistance is big, and electrons/ions conduction velocity is slower, and conductivity is small
In 10-10S/cm, more than two orders of magnitude also lower than LiFePO4.The energy gap that transition occurs in LiFePO4 for electronics is
0.3eV has characteristic of semiconductor；And the energy gap of lithium manganese phosphate is 2eV, electron conduction is poor, belongs to insulator.
For LiMnPO4Study on the modification generally uses carbon coating, metal ion mixing, three kinds of modes of material nanoization.Carbon
Cladding can effectively improve LiMnPO4The electric conductivity of particle.But LiMnPO4Surface coated carbon is inert matter, and carbon adds
The tap density and processing performance of material can not only be influenced by entering amount excessively, while reduce LiMnPO to a certain extent4With electricity
The contact area for solving liquid, hinders Li+Movement.And material electricity can both have been improved by using porous carbon materials to carry out open cladding
Electron conductivity does not influence Li again+Movement, the research for carrying out porous to cladding carbon material at present is also less, by carbon coated porous
It is to improve a very promising direction of material property.Currently, having done a lot of work in carbon coating process aspect.Example
Such as, Chinese patent (publication No. CNIO5390682A, date of publication 2016.03.09) discloses a kind of LiFePO4 microballoon/three-dimensional graphite
The preparation method of alkene combination electrode material, step are：It weighs 1g ferric phosphates and 1g glucose is scattered in 80ml deionized waters, set
120 DEG C of reaction 5h in 100ml hydrothermal reaction kettles wash dry obtained " spherical source of iron " polyhydroxy ferric phosphate microballoon.2g is more
Di iron microballoon (by ferrous metal quality), 0.3g lithium acetates (by lithium metal quality) and 0.6g graphene oxides are scattered in
It is dry in ionized water；Said mixture is placed in high temperature process furnances, carries out high temperature thermal response, reaction temperature in a nitrogen atmosphere
Degree is 750 DEG C, reaction time 8h, and heating rate is 2 DEG C/min；Obtain " LiFePO4Micro-/three-dimensional grapheme " composite wood
Material.Raw material first graphene oxide of the above method using graphene oxide as three-dimensional conductive skeleton expensive is unfavorable for work
Industry application, in addition the basic principle of above method structure three-dimensional grapheme is that layered graphite oxide alkene carries out in hydro-thermal reaction
Self assembly is assembled into three-dimensional cavernous structure by layer structure, but the above method is one-step method i.e. graphene oxide hydro-thermal self assembly
When can be influenced by other ions in solution, the three-dimensional grapheme structure easily caused is imperfect.Chinese patent (is announced
CNIO557622OA, publication date 2016.05.11) a kind of preparation of cellular carbon-coated LiFePO 4 for lithium ion batteries positive electrode, step are disclosed
It is：136.2g absolute ethyl alcohols are dissolved in 136.2g deionizations, pour into reaction kettle；Weigh 157gLiFePO4, 19.4g glucose
It is put into reaction kettle after mixing with 88.2g ammonium hydrogen carbonate, mixture is sufficiently stirred lh.Slurry after stirring evenly is put into very
In vacuum freecing-dry machine, freeze lh at -10 DEG C, then the dry 5h under vacuum 13Pa environment.Solid is put into 100 DEG C of bakings after drying
Case dries lh, the lower 750 DEG C of sintering 2h of nitrogen protection atmosphere.It is cooled to room temperature, 325 mesh sieve is crossed after grinding, obtains cellular carbon packet
Cover LiFePO4/C.The principle that the above method prepares porous carbon is that ammonium salt gas-phase decomposition progress pore-creating has obtained cellular carbon, still
Cellular carbon and LiFePO4The only other LiFePO of physical mixed4It is not present in the pore space structure of cellular carbon, cellular
Carbon only plays the role of electric action, can not play limitation grain size.
Invention content
The present invention is for LiMnPO present in current techniques4Material electronics poorly conductive, conventional packet carbon are in material table
Bread covers carbon material, serious polarization in this cladding mode material charge and discharge process, and big high rate performance is poor, it is proposed that using three-dimensional
Porous carbon skeleton is in LiMnPO4Three-dimensional conductive network is built between particle.The present invention can three-dimensional transmission electronics using three-dimensional porous carbon skeleton
Characteristic, increase electronics in LiMnPO4Transmission channel between particle, ensure while improving material electronics electrical conductivity it is higher from
Sub- conductivity.The not exclusively carbon-coated iron manganese phosphate for lithium of fractional open/three-dimensional carbon skeleton/carbon composite is constructed, material is reduced
Degree of polarization when charge and discharge improves chemical property.
Technical solution of the present invention is：
A kind of preparation method of three-dimensional carbon skeleton, includes the following steps：
1) carbon source, catalyst are added in ethyl alcohol and are stirred, then in 30-90 DEG C of vacuum drying, obtain mixture A；
Wherein, quality compares carbon source:Catalyst=5-50:1；Every gram of carbon source corresponds to 1-3ml ethyl alcohol；The carbon source is grape
It is one or more in sugar, sucrose, starch, oxalic acid, cellulose, ferrous gluconate, ferrous oxalate；Catalyst is ferrous sulfate, chlorine
Change one or more in iron, frerrous chloride, nickel sulfate, nickel chloride, cobaltous sulfate；
2) ball milling 1-9h after mixing mixture A obtained by step 1) with perforating agent, mass ratio are mixture A:Drilling
Agent=1:100-5000；Obtain mixture B；Rotational speed of ball-mill 100-500r/min；
3) by mixture B obtained by step 2), with infrared tablet press machine, in 1-50MPa pressure, 1-2g sizes are pressed into medicine next time
Piece；
4) tablet obtained by step 3) is sintered in an inert atmosphere, is included the following steps：
A, it is warming up to 350-400 DEG C under an inert atmosphere from room temperature with 2-5 DEG C/min heating rates, outlet temperature is known as
T1；And keep the temperature 60-120min at a temperature of T1；
B, it is warming up to 600-700 DEG C under an inert atmosphere from T1 with 1-4 DEG C/min heating rates, outlet temperature is known as T2；
60-180min is kept the temperature at a temperature of T2；
C, it is warming up to 700-900 DEG C under an inert atmosphere from T2 with 1-3 DEG C/min heating rates, outlet temperature is known as T3；
120-240min is kept the temperature at a temperature of T3；
D, 600-700 DEG C is cooled under an inert atmosphere from T3 with 0.2-1 DEG C/min rate of temperature fall, outlet temperature T4；
E, 500-600 DEG C is cooled under an inert atmosphere from T4 with 0.2-1 DEG C/min rate of temperature fall, outlet temperature T5；
F, 350-450 DEG C is cooled under an inert atmosphere from T5 with 1-1.5 DEG C/min rate of temperature fall, outlet temperature T6；
G, from T6, Temperature fall obtains mixture C to room temperature under an inert atmosphere；
Wherein inert atmosphere is nitrogen or argon gas atmosphere.
5) 4) mixture C obtained is put into distilled water, waits for that perforating agent is completely dissolved, solid is pulled out, after vacuum drying
Obtain three-dimensional carbon skeleton.
In the step 2) perforating agent be sodium chloride, potassium chloride, calcium chloride, lithium chloride, sodium carbonate, it is a kind of in calcium carbonate or
It is a variety of.
The present invention substantive distinguishing features be：
(its is simple for process, easy better than current three-dimensional ordered macroporous, three-dimensional meso-hole by being prepared to three-dimensional carbon skeleton by the present invention
The preparation of material), it is then used as the matrix of hydro-thermal reaction, the hole on three-dimensional carbon skeleton limits hydro-thermal to a certain extent
The growth of grain size in the process.On the other hand three-dimensional carbon skeleton has three-dimensional conductive compared with the one-dimensional carbon-coating that material surface routinely coats
Ability.
In the prior art, the presoma that prepared by hydro-thermal method coats one layer of agraphitic carbon (without fixed using carbon source in material surface
Type carbon conductive is poor), electronics conduction can only be contacted by the point-to-point between particle conducts.Or by presoma and graphene etc.
Lamella conductive material is compound, and conduction of the electronics point to face is achieved.And electronics may be implemented by point to three dimensions in the present invention
Conduction can improve the intergranular electronic conduction ability of positive electrode and reduce the enhancing positive electrode chemical property in turn that polarizes.
Beneficial effects of the present invention are：
The invention discloses a kind of preparation methods of iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite.Grape is mixed first
Sugar, ferrous sulfate then by mixture and sodium chloride ball milling, then use infrared tabletting machine, and chlorine is washed away after sintering is carbonized
Change sodium and three-dimensional carbon skeleton is made.Using obtained three-dimensional carbon skeleton as the matrix of iron manganese phosphate for lithium hydro-thermal reaction, iron manganese phosphate is prepared
Lithium/three-dimensional carbon skeleton/carbon composite.
The carbon source that is used when preparing three-dimensional carbon skeleton, catalyst, perforating agent are glucose common in industry, sulfuric acid Asia
The selection of iron, sodium chloride, the above raw material can reduce production cost.
When preparing three-dimensional carbon skeleton, using ferrous sulfate, there are two purposes：The micro addition of ferrous sulfate is with sintering first
Process is reduced into Fe simple substance by carbon simple substance, is a kind of structure of " nano island " under high temperature, when sintering in tube furnace program liter
Temperature is dissolved with program slow cooling process agraphitic carbon in this " nano island " structure to be precipitated mechanism and can improve the stone of carbon again
Blackization degree, and then enhance the electric conductivity of three-dimensional carbon skeleton.Secondly ferrous sulfate can enhance leading for carbon skeleton after being converted into Fe simple substance
Electrically.
In water-heat process iron manganese phosphate for lithium under the action of Gibbs free energy first on the hole wall of three-dimensional carbon skeleton at
Nucleus growth ultimately forms iron manganese phosphate for lithium/three-dimensional carbon skeleton structure, and due to being grown in aperture, three-dimensional carbon skeleton can play control
The effect of grain size.Presence additionally, due to three-dimensional carbon skeleton transferred out from iron manganese phosphate for lithium in discharge process it is electrically realized by
Point arrives the transmission of three dimensions, and this effective mechanisms of electronic can reduce the polarization phenomena in material charge and discharge process.
As described in Example 1, when it is iron manganese phosphate for lithium 3% that three-dimensional carbon skeleton quality, which is added, material compares under 0.1C multiplying powers
Capacity is that 160.2mAh/g reaches the 94.23% of theoretical specific capacity 170mAh/g, and specific capacity is after material circulation 30 times
151.8mAh/g, capacity retention ratio 94.47%.It is superior to same carbon content but is not added under the 0.1C multiplying powers of three-dimensional carbon frame material
155.8mAh/g, cycle 30 times after capacity retention ratio 91.91%.The quality that three-dimensional carbon skeleton is added is iron manganese phosphate for lithium 3%
When difference of the material under 0.1C multiplying powers between the charging platform and discharge platform of first charge-discharge for 0.1708V and not plus three-dimensional
The material platform difference of carbon skeleton is 0.2095V, and it is smaller that lower difference illustrates that material polarizes in charge and discharge.
Description of the drawings
Fig. 1 is that the SEM of the three-dimensional carbon skeleton and iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite obtained in embodiment 1 schemes；
Fig. 2 is obtained iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite and the phosphorus obtained in embodiment 3 in embodiment 1
Sour ferromanganese lithium/carbon composite material cycle charge-discharge curve graph；
Fig. 3 is obtained iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite and the phosphorus obtained in embodiment 3 in embodiment 1
Sour ferromanganese lithium/carbon composite material first charge-discharge curve graph；
Fig. 4 is the XRD spectra of obtained iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite in embodiment 1.
Specific implementation mode:
Present invention will be further explained below with reference to the attached drawings and examples.
The present invention water-heat process in reaction equation be：
3LiOH+XMnSO4+(1-X)FeSO4+H3PO4→LiMnxFe1-xPO4+Li2SO4+3H2O
Wherein X=0.1-0.9；
Embodiment 1：
1. manganese sulfate (0.0384mol), ferrous sulfate (0.0096mol), phosphoric acid (0.048mol), ascorbic acid
(0.014mol) presses LiMnxFe1-xPO4(X=0.8), 200ml water and ethylene glycol are dissolved in after weighing by volume=1:2 compositions
In the mixed solvent, referred to as A liquid；According to theoretical amount iron manganese phosphate for lithium:Three-dimensional carbon skeleton=1:0.03 mass ratio, by three-dimensional carbon skeleton
It is dispersed in water that 120ml contains lithium hydroxide (0.144mol) and ethylene glycol by volume=1:2 in the mixed solvents, magnetic agitation
12h obtains B liquid, and then B liquid 20min is added dropwise in A liquid and obtains the precursor solution of iron manganese phosphate for lithium, places it in high temperature height
It presses in reaction kettle, lithium concentration is 0.45mol/L in precursor solution；The volume of precursor solution is reactor volume
80%, 240 DEG C, reaction time 4h are heated to, with distilled water, each centrifuge washing of ethyl alcohol after reaction kettle cooled to room temperature
Iron manganese phosphate for lithium presoma is made after being dried in vacuo three times；
2. pressing presoma iron manganese phosphate for lithium:Glucose=15:4 mass ratio weighs glucose 0.8640g
Auxiliary agent 300r/min ball millings 6h.
3. by being put into tube furnace after the step 2. drying of gained mixture, it is sintered under atmosphere of inert gases, first at 350 DEG C
Under the conditions of pre-burning 3h, cool to room temperature with the furnace, then ground it is broken (until without the apparent blocky-shaped particle reunited together,
Following embodiment is same), it adds in tube furnace, is equally sintered under an inert atmosphere, sintering process is respectively 650 DEG C, 6h, with stove
It is cooled to room temperature, finally obtains the iron manganese phosphate for lithium composite material for being constituted three-dimensional conductive network with three-dimensional carbon skeleton and carbon；
Wherein, inert atmosphere is nitrogen atmosphere.
Phosphorus content is the 9% of iron manganese phosphate for lithium quality in final product, and 9% carbon is respectively from being added in water-heat process
Carbon 6% after the glucose carbonization that 3% three-dimensional carbon skeleton is added with presoma mechanical milling process.
The preparation method of the three-dimensional carbon skeleton, includes the following steps：
1) by glucose, ferrous sulfate in mass ratio 22:1, it is sufficiently stirred and is scattered in ethyl alcohol (every gram of carbon source corresponds to 1.5ml
Ethyl alcohol) in, 60 DEG C of vacuum drying obtain mixture A；
2) by mixture A obtained by step 1) and sodium chloride in mass ratio 1:240,300r/min ball milling 6h, obtain mixture
B；
3) mixture B obtained by step 2) is depressed into tablet with infrared tablet press machine in 1g pressure of 20MPa；
4) tablet obtained by step 3) is sintered in an inert atmosphere, processing step is：
A, heating process is warming up to 400 DEG C under an inert atmosphere from room temperature with 4 DEG C/min heating rates, and outlet temperature claims
For T1；And keep the temperature 60min at a temperature of T1；
B, heating process is warming up to 650 DEG C under an inert atmosphere from T1 with 2 DEG C/min heating rates, and outlet temperature is known as
T2；And keep the temperature 120min at a temperature of T2；
C, heating process is warming up to 750 DEG C under an inert atmosphere from T2 with 1 DEG C/min heating rates, and outlet temperature is known as
T3；And keep the temperature 180min at a temperature of T3；
D, temperature reduction technology cools to 650 DEG C under an inert atmosphere from T3 with 0.5 DEG C/min rate of temperature fall, and outlet temperature is
T4；
E, temperature reduction technology cools to 550 DEG C, outlet temperature T5 under an inert atmosphere from T4 with 1 DEG C/min rate of temperature fall；
F, temperature reduction technology cools to 400 DEG C under an inert atmosphere from T5 with 1.5 DEG C/min rate of temperature fall, and outlet temperature is
T6；
G, temperature reduction technology, from T6, Temperature fall obtains mixture C to room temperature under an inert atmosphere；
Wherein inert atmosphere is nitrogen atmosphere.
5) 4) mixture C obtained is put into distilled water, wait for perforating agent be completely dissolved (distilled water that more renews of midway,
A small amount of distilled water for impregnating three-dimensional carbon skeleton is taken to instill AgNO3Solution, no white precipitate generate, it was demonstrated that perforating agent is completely dissolved), fishing
Go out solid, three-dimensional carbon skeleton is obtained after vacuum drying.
It can be seen that the three-dimensional carbon skeleton prepared by the present invention shows irregular three-dimensional aperture layer structure, hole from a in Fig. 1
Diameter is between 100nm-1 μm, and iron manganese phosphate for lithium particle is grown in three-dimensional carbon frame aperture hole after hydro-thermal reaction, and grain size is in 100nm-
Between 300nm.The three-dimensional carbon skeleton that iron manganese phosphate for lithium is capable of multi-path conduction not exclusively coats, and it is incomplete to construct fractional open
On the one hand the addition of carbon-coated iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite, three-dimensional carbon skeleton limits phosphorus in water-heat process
The undue growth of sour ferromanganese lithium material particle, on the other hand enhances the electric conductivity between material granule.
Fig. 2 is to carry out charge-discharge test performance curve to battery using CT2001A type LAND testers, and voltage range is
2.0-4.6V, 25 DEG C of test temperature.It can be seen that 3%+6% carbon of three-dimensional carbon skeleton is added under 0.1C multiplying powers, (glucose is carbonized
) iron manganese phosphate for lithium specific capacity can reach 160.2mAh/g, and use identical preparation process that 9% carbon (grape is only added
Sugar charcoal-embodiment 3) lithium ferric manganese phosphate 0.1C multiplying powers under specific capacity be 155.8mAh/g.
Fig. 3 is to carry out charge-discharge test curve, voltage range 2.0- to battery using CT2001A type LAND testers
4.6V, 25 DEG C of test temperature.It can be seen that the phosphorus of 3% three-dimensional+6% carbon of carbon skeleton (glucose carbonization) is added under 0.1C multiplying powers
Difference between sour ferromanganese lithium charge and discharge platform is 0.1708V, and uses identical preparation process that 9% carbon (glucose is only added
Carbonization-
Embodiment 3) lithium ferric manganese phosphate 0.1C multiplying powers under difference between charge and discharge platform be 0.2095V, illustrate to be added
Three-dimensional carbon skeleton reduces the polarization phenomena of material.
Fig. 4 can be seen that a process for preparing the XRD spectra of iron manganese phosphate for lithium match with standard spectrogram, and peak type
Sharp free from admixture peak occurs, and the complete iron manganese phosphate lithium material of crystal form can be prepared by explanation this method.
Embodiment 2：
1. by manganese sulfate (0.0096mol), ferrous sulfate (0.0384mol), phosphoric acid (0.048mol), ascorbic acid
(0.018mol) presses LiMnxFe1-xPO4(X=0.2) 200ml water and ethylene glycol are dissolved in after weighing by volume=1:2 compositions
In the mixed solvent, referred to as A liquid；According to theoretical amount iron manganese phosphate for lithium:Three-dimensional carbon skeleton=1:0.1 mass ratio disperses three-dimensional carbon skeleton
120ml contain lithium hydroxide (0.1584mol) water and ethylene glycol by volume=1:2 in the mixed solvents, magnetic agitation 10h
B liquid is obtained, then B liquid 15min is added dropwise in A liquid and obtains the precursor solution of iron manganese phosphate for lithium, places it in high temperature and pressure
In reaction kettle, lithium concentration is 0.495mol/L in precursor solution；The volume of precursor solution is reactor volume
60%, 200 DEG C, reaction time 6h are heated to, with distilled water, each centrifuge washing of ethyl alcohol after reaction kettle cooled to room temperature
Iron manganese phosphate for lithium presoma is made after being dried in vacuo three times；
2. pressing presoma iron manganese phosphate for lithium:Glucose=15:It is to help that 8 mass ratio, which weighs glucose 0.8640g with ethyl alcohol,
Agent 400r/min ball millings 1h.
3. by being put into tube furnace after the step 2. drying of gained mixture, it is sintered under atmosphere of inert gases, first at 390 DEG C
Under the conditions of pre-burning 2h, cool to room temperature with the furnace, then ground broken, add in tube furnace, equally under an inert atmosphere
Sintering, sintering process is respectively 700 DEG C, and 4h cools to room temperature with the furnace, finally obtains and is constituted three-dimensional conductive with three-dimensional carbon skeleton and carbon
The iron manganese phosphate for lithium composite material of network；
Wherein, inert atmosphere is argon gas atmosphere.
Phosphorus content is the 22% of iron manganese phosphate for lithium quality in final product, and 22% carbon is respectively from being added in water-heat process
Carbon 12% after the glucose carbonization that 10% carbon skeleton is added with presoma mechanical milling process.
The preparation method of the three-dimensional carbon skeleton, includes the following steps：
1) by ferrous gluconate, cobaltous sulfate in mass ratio 10:1, it is sufficiently stirred and is scattered in ethyl alcohol (every gram of carbon source correspondence
2ml ethyl alcohol) in, 50 DEG C of vacuum drying obtain mixture A；
2) by mixture A obtained by step 1) and sodium carbonate in mass ratio 1:1000,200r/min ball milling 4h, obtain mixture
B；
3) by with infrared tablet press machine, in 10MPa pressure, 1.5g is pressed into tablet to mixture B next time obtained by step 2)；
4) tablet obtained by step 3) is sintered in an inert atmosphere, processing step is：
A, heating process is warming up to 350 DEG C under an inert atmosphere from room temperature with 5 DEG C/min heating rates, and outlet temperature claims
For T1；And keep the temperature 120min at a temperature of T1；
B, heating process is warming up to 700 DEG C under an inert atmosphere from T1 with 1 DEG C/min heating rates, and outlet temperature is known as
T2；And keep the temperature 180min at a temperature of T2；
C, heating process is warming up to 800 DEG C under an inert atmosphere from T2 with 2 DEG C/min heating rates, and outlet temperature is known as
T3；And keep the temperature 240min at a temperature of T3；
D, temperature reduction technology cools to 700 DEG C under an inert atmosphere from T3 with 0.2 DEG C/min rate of temperature fall, and outlet temperature is
T4；
E, temperature reduction technology cools to 600 DEG C under an inert atmosphere from T4 with 0.5 DEG C/min rate of temperature fall, and outlet temperature is
T5；
F, temperature reduction technology cools to 350 DEG C, outlet temperature T6 under an inert atmosphere from T5 with 1 DEG C/min rate of temperature fall；
G, temperature reduction technology, from T6, Temperature fall obtains mixture C to room temperature under an inert atmosphere；
Wherein inert atmosphere argon gas atmosphere.
5) 4) mixture C obtained is put into distilled water, wait for perforating agent be completely dissolved (distilled water that more renews of midway,
A small amount of distilled water for impregnating three-dimensional carbon skeleton is taken to instill AgNO3Solution, no precipitation generate, it was demonstrated that perforating agent is completely dissolved), it pulls out solid
Body obtains three-dimensional carbon skeleton after vacuum drying.
Embodiment 3：
1. manganese sulfate (0.0384mol), ferrous sulfate (0.0096mol), phosphoric acid (0.048mol), ascorbic acid
(0.014mol) presses LiMnxFe1-xPO4(X=0.8).200ml water and ethylene glycol are dissolved in after weighing by volume=1:2 compositions
In the mixed solvent, referred to as A liquid；Lithium hydroxide (0.144mol) is dispersed in water that 120ml contains and ethylene glycol by volume
=1:2 in the mixed solvents obtain B liquid, and then B liquid 20min is added dropwise in A liquid and obtains the precursor solution of iron manganese phosphate for lithium,
It places it in high-temperature high-pressure reaction kettle, lithium concentration is 0.45mol/L in precursor solution；The volume of precursor solution is
The 80% of reactor volume is heated to 240 DEG C, reaction time 4h, with distilled water, second after reaction kettle cooled to room temperature
Iron manganese phosphate for lithium presoma is made after being dried in vacuo three times in each centrifuge washing of alcohol；
2. pressing presoma iron manganese phosphate for lithium:Glucose=5:2 mass ratio weighs glucose 0.7960g using ethyl alcohol as auxiliary agent
300r/min ball millings 6h.
3. by being put into tube furnace after the step 2. drying of gained mixture, it is sintered under atmosphere of inert gases, first at 350 DEG C
Under the conditions of pre-burning 3h, cool to room temperature with the furnace, then ground broken, add in tube furnace, equally under an inert atmosphere
Sintering, sintering process is respectively 650 DEG C, and 6h cools to room temperature with the furnace, finally obtains manganese phosphate lithium/carbon composite material；
Wherein, inert atmosphere is nitrogen atmosphere.
Phosphorus content is the 9% of iron manganese phosphate for lithium quality in final product.
Unaccomplished matter of the present invention is known technology.
Claims (2)
1. a kind of preparation method of three-dimensional carbon skeleton, it is characterized in that including the following steps：
1）Carbon source, catalyst are added in ethyl alcohol and are stirred, then in 30-90 DEG C of vacuum drying, obtains mixture A；
Wherein, quality compares carbon source:Catalyst=5-50:1；Every gram of carbon source corresponds to 1-3ml ethyl alcohol；The carbon source is glucose, sugarcane
It is one or more in sugar, starch, oxalic acid, cellulose, ferrous gluconate, ferrous oxalate；Catalyst be ferrous sulfate, iron chloride,
It is one or more in frerrous chloride, nickel sulfate, nickel chloride, cobaltous sulfate；
2) ball milling 1-9h after mixing mixture A obtained by step 1) with perforating agent, mass ratio are mixture A:Perforating agent=1:
100-5000；Obtain mixture B；Rotational speed of ball-mill 100-500r/min；
3) by mixture B obtained by step 2), with infrared tablet press machine, in 1-50MPa pressure, 1-2g sizes are pressed into tablet next time；
4) tablet obtained by step 3) is sintered in an inert atmosphere, is included the following steps：
A, it is warming up to 350-400 DEG C under an inert atmosphere from room temperature with 2-5 DEG C/min heating rates, outlet temperature is known as T1；And
60-120min is kept the temperature at a temperature of T1；
B, it is warming up to 600-700 DEG C under an inert atmosphere from T1 with 1-4 DEG C/min heating rates, outlet temperature is known as T2；In T2
At a temperature of keep the temperature 60-180min；
C, it is warming up to 700-900 DEG C under an inert atmosphere from T2 with 1-3 DEG C/min heating rates, outlet temperature is known as T3；In T3
At a temperature of keep the temperature 120-240min；
D, 600-700 DEG C is cooled under an inert atmosphere from T3 with 0.2-1 DEG C/min rate of temperature fall, outlet temperature T4；
E, 500-600 DEG C is cooled under an inert atmosphere from T4 with 0.2-1 DEG C/min rate of temperature fall, outlet temperature T5；
F, 350-450 DEG C is cooled under an inert atmosphere from T5 with 1-1.5 DEG C/min rate of temperature fall, outlet temperature T6；
G, from T6, Temperature fall obtains mixture C to room temperature under an inert atmosphere；
Wherein inert atmosphere is nitrogen or argon gas atmosphere；
5）By 4）In obtained mixture C input distilled water, waits for that perforating agent is completely dissolved, pull solid out, obtained after vacuum drying
Three-dimensional carbon skeleton.
2. the preparation method of three-dimensional carbon skeleton as described in claim 1, it is characterized in that the step 2）Middle perforating agent is chlorination
It is one or more in sodium, potassium chloride, calcium chloride, lithium chloride, sodium carbonate and calcium carbonate.
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| CN107482217B (en) * | 2017-08-08 | 2019-12-17 | 四川朗晟新能源科技有限公司 | preparation method of modified lithium iron manganese phosphate |
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| CN110690424A (en) * | 2019-09-27 | 2020-01-14 | 天津大学 | Preparation method of three-dimensional carbon-coated nano lithium iron phosphate lithium ion battery positive electrode material |
| CN115275170B (en) * | 2022-09-02 | 2023-06-30 | 永州昊利新材料科技有限公司 | Preparation method of cerium dioxide modified lithium iron manganese phosphate electrode material |
| CN115676794B (en) * | 2022-10-24 | 2024-01-09 | 广东邦普循环科技有限公司 | Method for preparing lithium iron manganese phosphate positive electrode material by coprecipitation and application thereof |
| CN116354325A (en) * | 2022-12-26 | 2023-06-30 | 蜂巢能源科技(无锡)有限公司 | Positive electrode material, preparation method thereof and lithium ion battery |
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