CN108417814A - A kind of lithium cell cathode material and preparation method of organic lithium salt prelithiation - Google Patents
A kind of lithium cell cathode material and preparation method of organic lithium salt prelithiation Download PDFInfo
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Abstract
The present invention relates to a kind of lithium cell cathode materials and preparation method of organic lithium salt prelithiation, belong to lithium cell cathode material technical field.The technical problem to be solved by the present invention is to provide a kind of lithium cell cathode materials and preparation method thereof of organic lithium salt prelithiation, rich lithium organic matter is obtained by the reaction by lithium source and the organic solvent containing hydroxyl and itrile group, negative material is coated by rich lithium organic matter again, obtains the lithium cell cathode material of organic lithium salt prelithiation.Its method is simple, and without relying on special raw material and equipment, cost is relatively low, use easy to spread.The negative material obtained by this method, it can be during first charge-discharge, it is fallen off by the rich lithium oxidation operation of negative terminal surface and is reconstructed into SEI films, reduce the consumption of lithium source in positive electrode, to improve cycle efficieny for the first time, solve the problems, such as traditional ternary lithium battery follow for the first time bad efficiency decay it is serious.
Description
Technical field
The present invention relates to a kind of lithium cell cathode materials and preparation method of organic lithium salt prelithiation, belong to cathode of lithium battery
Field of material technology.
Background technology
Lithium ion battery is a kind of secondary cell（That is rechargeable battery）, it rely primarily on lithium ion anode and cathode it
Between it is mobile come work.In charge and discharge process, Li+Round-trip insertion and deintercalation between two electrodes：When charging, Li+From anode
Deintercalation is embedded in cathode by electrolyte, and cathode is in rich lithium state；It is then opposite when electric discharge.Lithium ion battery has light-weight, storage
Can be big, power is big, pollution-free the features such as, also more and more extensive in the application of every field, its research and production all achieves
Prodigious progress.With traditional accumulator comparatively, lithium ion battery not only energy higher, discharge capability is stronger, the longevity is recycled
Order longer, therefore, lithium ion battery is high all the way with the development of electric vehicle, has become the master of electric powered motor at present
Want source.Its type is various, with their own characteristics, is all difficult to be replaced by other power in following long period.
Anode material for lithium-ion batteries main study subject is tertiary cathode material at present, and main advantage is high power capacity
With stable cryogenic property.But its disadvantage is also relatively apparent：Cationic mixing is serious；Poor high temperature stability；Loop attenuation for the first time
It is serious etc..For disadvantages described above, this field scientific research personnel has done a large amount of research.
It discloses a kind of surface of anode material for lithium-ion batteries application No. is 201610116860.0 patent of invention and changes
Property method, including by crush after anode material for lithium-ion batteries be added to the mixed solution being made of cerous nitrate and neodymium nitrate
In, it adds after ammonium hydroxide mixed, ultrasonic agitation, evaporable water and drying；It is pressed into piece after dry product is ground
Shape sample, then sheet sample is put into and is continuously passed through in the tube furnace of oxygen, it first heats up and is calcined in oxygen, then in argon gas
Calcine finished product.The lithium electricity positive electrode of the invention passes through the coating modification of neodymium dopen Nano ceria, maintains structure
Stability improves its cycle efficieny for the first time, and fills up the oxygen defect generated due to lithium ion deintercalation to maintain material structure
Stablize, while coating passes through surface-hydrophobicized processing, there is stronger anti-water absorbing capacity.
Application No. is 201310548457.1 patents of invention to disclose a kind of lithium ion battery negative material carbon cladding
3 SiC 2/graphite and preparation method thereof, the negative material are made of silicon, graphite and amorphous carbon, and wherein silicon particle is adhered to graphite particle
Surface, amorphous carbon layer are coated on the surface of silicon and graphite.Preparation method is to be sufficiently mixed silicon, graphite and carbon source uniformly, drying
High temperature sintering certain time under the conditions of inert gas shielding is placed in high temperature reaction stove, you can obtains carbon-coated 3 SiC 2/graphite
Negative material.The negative material is provided simultaneously with excellent cyclical stability, high cycle coulombic efficiency and excellent multiplying power for the first time
Cycle performance has comprehensive chemical property.The preparation process of the present invention is simple, is easy to industrialized mass production, and do not deposit
It is environmentally protective in environmental pollution.
Application No. is 201110378735.4 patent of invention disclose a kind of lithium ion battery silicon-carbon cathode material and its
Preparation method, technical problems to be solved are to improve the charge and discharge cycles stability of electrode material.The invention is compound by silicon-carbon
Material is mixed with natural graphite class material, and the quality of Si-C composite material is 7~20%；Si-C composite material is by carbon nanotube
And/or carbon nano-fiber deposits to nano silica fume particle surface and/or is embedded between nano silica fume particle and forms core, in core
Surface is coated with carbon-coating, carbon-coating quality 3~15%.Preparation method includes：Prepare presoma silica flour, chemical vapor deposition, liquid phase
Cladding roasting, crushes, mixing.Compared with prior art, silicon-carbon composite cathode material reversible specific capacity is more than 500mAh/ for the invention
G recycles coulombic efficiency and is more than 80% for the first time, recycles 50 weeks capacity retention ratios more than 95%, preparation process is simple, it is easily operated,
It is of low cost, suitable for all kinds of portable device lithium ion battery negative materials of high capacity type.
To sum up, solve to discharge for the first time at present decaying main method be in positive/negative surface coated lithium ion separation layer, from
And control the thickness of SEI films.And be mostly the direct lithiumation of electrolyte for the prelithiation material of cathode, there has been no mended by lithium ion
It repays mechanism and alleviates Capacity fading problem for the first time.
Invention content
For disadvantages described above, the present invention proposes lithium cell cathode material and its preparation side of a kind of organic lithium salt prelithiation
Method alleviates Capacity fading problem for the first time by lithium ion compensation mechanism.
First technical problem that the present invention solves is to provide a kind of lithium cell cathode material of organic lithium salt prelithiation
Preparation method.
A kind of preparation method of the lithium cell cathode material of organic lithium salt prelithiation, includes the following steps：
A, the preparation of covering material：In an inert atmosphere, it by the organic compound mixing of lithium source and hydroxyl and itrile group, is heated to
160~250 DEG C of 4~8h of reaction replace the hydrogen atom of hydroxyl to form Li-O keys, obtain covering material by substitution reaction；It is described
Organic compound is the aromatic compound containing hydroxyl and mononitrile base simultaneously；And the hydroxyl in the lithium and organic compound in lithium source
The molar ratio of base is 1~2:1；
B, coating modification：Covering material is heated and is melted, 5~40% that covering material addition is negative material weight are then pressed
Negative material is added in covering material, with the rotating speed of 800~5000r/min, 10~50min is mixed, naturally cools to room temperature, obtain
To the lithium cell cathode material of organic lithium salt prelithiation.
The method of the present invention is obtained by the reaction rich lithium organic matter by lithium source and the organic solvent containing hydroxyl and itrile group, then leads to
It crosses rich lithium organic matter to coat negative material, obtains the lithium cell cathode material of organic lithium salt prelithiation.The material is in head
It in secondary charge and discharge process, is fallen off by the rich lithium oxidation operation of negative terminal surface and is reconstructed into SEI films, reduce lithium source in positive electrode
Consumption, to improve cycle efficieny for the first time, solve the problems, such as traditional ternary lithium battery follow for the first time bad efficiency decay it is serious.
A steps mainly prepare rich lithium organic matter as covering material.In an inert atmosphere, by lithium source and hydroxyl and nitrile
The organic compound mixing of base is heated to 160~250 DEG C of 4~8h of reaction, replaces the hydrogen atom of hydroxyl to be formed by substitution reaction
Li-O keys, obtain covering material；The organic compound is the aromatic compound for containing more than two hydroxyls and mononitrile base simultaneously
Object；And the molar ratio of the hydroxyl in the lithium and organic compound in lithium source is 1~2:1.
In theory, as long as the aromatic compound containing more than two hydroxyls and an itrile group is suitable for this
Invention.In order to improve the preparation efficiency of rich lithium organic matter, and also to improve the lithium electricity of final product organic lithium salt prelithiation
The performance of pond negative material, it is preferred that the organic compound is 3,4- dihydroxybenzonitriles.
3,4- dihydroxybenzonitriles also make 3,4- dihydroxy cyanophenyl or 4- cyano catechols, CAS be encoded to 17345-
61-8, containing there are two hydroxyl and an itrile group in molecular structure, fusing point is 154~156 DEG C, boiling point at one atm
It it is 334.8 DEG C, the present invention is reacted using 3,4- dihydroxybenzonitriles with lithium source, by substitution reaction by the hydrogen atom of hydroxyl
It is replaced by lithium, forms Li-O keys.
3,4- dihydroxybenzonitriles of the present invention may be used commercially available, can also select homemade, 3,4- dihydroxy
The prior art may be used in the preparation method of benzonitrile.Preferably, 3, the 4- dihydroxybenzonitriles use such as lower section
It is prepared by method：Using -4 hydroxy benzaldehyde of 3- methoxyl groups as raw material, 3,4- 4-dihydroxy benzaldehydes are synthesized by hydroxyl substitution reaction, it
It is heated to 40 DEG C in water afterwards, hydroxylamine hydrochloride, sodium acetate is added, be warming up to 80 DEG C of stirring 2h, methyl is used after being cooled to room temperature
Tertbutyl ether extracts, and by obtaining 3,4- dihydroxy benzenes first oxime crude products after washing, drying, drying, crude product is dissolved in chloroform, is cooled down
To 0 DEG C, the chloroformic solution of diethyl phosphorous acyl chlorides is added dropwise, is warmed to room temperature removes chloroform and residue later, washs drying, finally
3,4- dihydroxybenzonitriles are obtained by ethyl acetate purifying.
Lithium source is the substance with hydroxyl and the organic compound reaction of itrile group, it is preferred that the lithium source is lithium metal.
Since lithium source can react in air, for example, lithium metal can be reacted with the nitrogen in air generates lithium nitride,
It is reacted with oxygen and generates lithia, therefore, a steps need to carry out in an inert atmosphere.Preferably, the inert atmosphere is helium
Gas, neon, argon gas, Krypton or xenon, in order to reduce cost, the preferably described inert atmosphere is argon gas.
The proportioning of the hydroxyl in lithium and organic compound in lithium source will influence the generation of rich lithium compound, study table
It is bright, when the molar ratio of the hydroxyl in the lithium and organic compound in lithium source is 1~2:When 1, obtained final products organic lithium salt
The better performances of the lithium cell cathode material of prelithiation, therefore, the present invention select the hydroxyl in lithium and organic compound in lithium source
The molar ratio of base is 1~2:1.Preferably, the molar ratio of the hydroxyl in the lithium and organic compound in lithium source is 1.2:
1, the performance of the lithium cell cathode material for the organic lithium salt prelithiation which is prepared is best.
Reaction temperature and time also have a certain impact to reaction, preferably, in a steps, are heated to 210 DEG C instead
6h is answered, the performance of the lithium cell cathode material of the organic lithium salt prelithiation obtained at this time is best.
Covering material is heated and is melted by the step of b step is coating modification, and temperature ensures that melting is complete, selects 160
It is DEG C best.Then negative material is added in covering material by 5~40% that covering material addition is negative material weight, with 800
The rotating speed of~5000r/min mixes 10~50min, room temperature is naturally cooled to, by rich lithium Coated with Organic Matter on negative material surface
Obtain the lithium cell cathode material of organic lithium salt prelithiation.
Negative material commonly used in the art is suitable for the present invention, it is preferred that the negative material is carbon-based material or silicon
Sill.It is furthermore preferred that the negative material selects porous carbon materials.
The proportioning of negative material and covering material will influence the thickness of clad and the effect of cladding, hair of the invention
A person of good sense in the covering material of melting the study found that be added negative material, if the addition of negative material is too low, it will cause
Clad is thicker, influences the chemical property of the lithium cell cathode material of organic lithium salt prelithiation, and the addition of negative material
If excessively high, covered effect is poor, or even cladding can be caused incomplete, can not solve the problems, such as to follow for the first time bad efficiency decay it is serious.
Therefore, by 20% that covering material addition is negative material weight that covering material addition negative material performance is best.
After negative material being added in the covering material of melting, needing to be stirred makes it be uniformly dispersed, to improve
The uniformity of cladding.Preferably, with the rotating speed of 2000r/min, 30min is mixed.
Second technical problem that the present invention solves is to provide a kind of lithium cell cathode material of organic lithium salt prelithiation.
The lithium cell cathode material of organic lithium salt prelithiation of the present invention, adopts and is prepared with the aforedescribed process.The organolithium
The lithium cell cathode material surface of salt prelithiation is coated with rich lithium organic matter, for example 3,4- dihydroxybenzonitriles two are contained on surface
Lithium, during first charge-discharge, 3, the 4- dihydroxybenzonitriles on the lithium cell cathode material surface of the organic lithium salt prelithiation
Two lithiums, which will aoxidize to fall off, is reconstructed into SEI films, to reduce the consumption of lithium source in positive electrode, improves cycle efficieny for the first time.
Compared with prior art, the present invention has the advantages that：
The method of the present invention is obtained by the reaction rich lithium organic matter by lithium source and the organic solvent containing hydroxyl and itrile group, then passes through
Rich lithium organic matter coats negative material, obtains the lithium cell cathode material of organic lithium salt prelithiation.Its method is simple, nothing
Special raw material and equipment need to be relied on, cost is relatively low, use easy to spread.
The lithium cell cathode material of organic lithium salt prelithiation of the present invention can pass through cathode during first charge-discharge
The rich lithium oxidation operation on surface, which falls off, is reconstructed into SEI films, reduces the consumption of lithium source in positive electrode, is recycled for the first time to improve
Efficiency.Solve the problems, such as traditional ternary lithium battery follow for the first time bad efficiency decay it is serious, can suitable for lithium ion battery
Improve the cycle performance of lithium ion battery.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The lithium cell cathode material of organic lithium salt prelithiation is prepared with the following method：
A, the preparation of covering material：In inert gas argon gas atmosphere, by organising for lithium source lithium metal and hydroxyl and itrile group
Object 3 is closed, 4- dihydroxybenzonitrile mixings are heated to 160 DEG C of reaction 4h, replace the hydrogen atom of hydroxyl to be formed by substitution reaction
Li-O keys, obtain covering material；The molar ratio of the hydroxyl in lithium and organic compound in lithium source is 1:1；Wherein, described 3,4-
Dihydroxybenzonitrile is prepared with the following method：Using -4 hydroxy benzaldehyde of 3- methoxyl groups as raw material, pass through hydroxyl substitution reaction
3,4- 4-dihydroxy benzaldehydes are synthesized, are heated to 40 DEG C in water later, hydroxylamine hydrochloride and sodium acetate is added, is warming up to 80 DEG C of stirrings
2h is extracted after being cooled to room temperature using methyl tertiary butyl ether(MTBE), by obtaining 3,4- dihydroxy benzenes first oximes after washing, drying, drying
Crude product is dissolved in chloroform by crude product, is cooled to 0 DEG C, and the chloroformic solution of diethyl phosphorous acyl chlorides is added dropwise, is warmed to room temperature later except dechlorination
Imitative and residue washs drying, is purified finally by ethyl acetate and obtains 3,4- dihydroxybenzonitriles.
B, coating modification：Covering material is heated and is melted, 5% that covering material addition is negative material weight is then pressed
Negative material is added in covering material, the negative material is carbon-based material；With the rotating speed of 800r/min, 10min is mixed, it is natural
It is cooled to room temperature, obtains the lithium cell cathode material of organic lithium salt prelithiation.
Using the lithium cell cathode material of the organic lithium salt prelithiation of preparation as lithium ion battery negative material, it is carried out
Charge and discharge and cycle performance test：The lithium cell cathode material of organic lithium salt prelithiation and conductive agent, binder in mass ratio 8:
1:1 mixing, is coated on 0.01mm copper foils, electrode slice is made as working electrode；811 type nickle cobalt lithium manganates are prepared into electrode conduct
Anode, electrolyte solvent are EC and the mixed solvent of DMC, and the volume ratio of the two is 1:1, LiFP6 as electrolyte lithium salt, dense
Degree is 1mol/L, and diaphragm used is PP (Celgard2400), and button cell, and button type are assembled in argon gas atmosphere glove box
Battery carries out charge-discharge test, and current density is 0.1C (1C:2000mA/g).The lithium ion battery anode material of the organic lithium salt prelithiation
Expect 500 cyclical stabilities at 0.1C and and coulombic efficiency is shown in Table 1 for the first time.
Embodiment 2
The lithium cell cathode material of organic lithium salt prelithiation is prepared with the following method：
A, the preparation of covering material：In inert gas argon gas atmosphere, by organising for lithium source lithium metal and hydroxyl and itrile group
Object 3 is closed, 4- dihydroxybenzonitrile mixings are heated to 250 DEG C of reaction 8h, replace the hydrogen atom of hydroxyl to be formed by substitution reaction
Li-O keys, obtain covering material；The molar ratio of the hydroxyl in lithium and organic compound in lithium source is 2:1；Wherein, described 3,4-
Dihydroxybenzonitrile is using commercially available.
B, coating modification：Covering material is heated and is melted, 40% that covering material addition is negative material weight is then pressed
Negative material is added in covering material, the negative material is silica-base material；With the rotating speed of 5000r/min, 50min is mixed, from
It so is cooled to room temperature, obtains the lithium cell cathode material of organic lithium salt prelithiation.
Using the lithium cell cathode material of the organic lithium salt prelithiation of preparation as lithium ion battery negative material, it is carried out
Charge and discharge and cycle performance test, test method is referring to embodiment 1.
Embodiment 3
The lithium cell cathode material of organic lithium salt prelithiation is prepared with the following method：
A, the preparation of covering material：In inert gas argon gas atmosphere, by organising for lithium source lithium metal and hydroxyl and itrile group
Object 3 is closed, 4- dihydroxybenzonitrile mixings are heated to 180 DEG C of reaction 5h, replace the hydrogen atom of hydroxyl to be formed by substitution reaction
Li-O keys, obtain covering material；The molar ratio of the hydroxyl in lithium and organic compound in lithium source is 1.1:1；Wherein, described 3,
4- dihydroxybenzonitriles are using commercially available.
B, coating modification：Covering material is heated and is melted, 10% that covering material addition is negative material weight is then pressed
Negative material is added in covering material, the negative material is carbon-based material；With the rotating speed of 4000r/min, 15min is mixed, from
It so is cooled to room temperature, obtains the lithium cell cathode material of organic lithium salt prelithiation.
Using the lithium cell cathode material of the organic lithium salt prelithiation of preparation as lithium ion battery negative material, it is carried out
Charge and discharge and cycle performance test, test method is referring to embodiment 1.
Embodiment 4
The lithium cell cathode material of organic lithium salt prelithiation is prepared with the following method：
A, the preparation of covering material：In inert gas argon gas atmosphere, by organising for lithium source lithium metal and hydroxyl and itrile group
Object 3 is closed, 4- dihydroxybenzonitrile mixings are heated to 230 DEG C of reaction 5h, replace the hydrogen atom of hydroxyl to be formed by substitution reaction
Li-O keys, obtain covering material；The molar ratio of the hydroxyl in lithium and organic compound in lithium source is 1.6:1；Wherein, described 3,
4- dihydroxybenzonitriles are using commercially available.
B, coating modification：Covering material is heated and is melted, 30% that covering material addition is negative material weight is then pressed
Negative material is added in covering material, the negative material is carbon-based material；With the rotating speed of 3000r/min, 20min is mixed, then
With the heating rate of 3 DEG C/min to 800 DEG C, 11h is roasted, room temperature is naturally cooled to, obtains the lithium battery of organic lithium salt prelithiation
Negative material.
Using the lithium cell cathode material of the organic lithium salt prelithiation of preparation as lithium ion battery negative material, it is carried out
Charge and discharge and cycle performance test, test method is referring to embodiment 1.
Embodiment 5
The lithium cell cathode material of organic lithium salt prelithiation is prepared with the following method：
A, the preparation of covering material：In inert gas argon gas atmosphere, by organising for lithium source lithium metal and hydroxyl and itrile group
Object 3 is closed, 4- dihydroxybenzonitrile mixings are heated to 240 DEG C of reaction 7h, replace the hydrogen atom of hydroxyl to be formed by substitution reaction
Li-O keys, obtain covering material；The molar ratio of the hydroxyl in lithium and organic compound in lithium source is 1.5:1；Wherein, described 3,
4- dihydroxybenzonitriles are prepared with the following method：Using -4 hydroxy benzaldehyde of 3- methoxyl groups as raw material, replaced by hydroxyl anti-
3,4- 4-dihydroxy benzaldehydes should be synthesized, are heated to 40 DEG C in water later, hydroxylamine hydrochloride and sodium acetate is added, is warming up to 80 DEG C and stirs
2h is mixed, is extracted using methyl tertiary butyl ether(MTBE) after being cooled to room temperature, by obtaining 3,4- dihydroxy benzenes first after washing, drying, drying
Crude product is dissolved in chloroform by oxime crude product, is cooled to 0 DEG C, and the chloroformic solution of diethyl phosphorous acyl chlorides is added dropwise, is warmed to room temperature removing later
Chloroform and residue wash drying, are purified finally by ethyl acetate and obtain 3,4- dihydroxybenzonitriles.
B, coating modification：Covering material is heated and is melted, 25% that covering material addition is negative material weight is then pressed
Negative material is added in covering material, the negative material is carbon-based material；With the rotating speed of 2500r/min, 30min is mixed, from
It so is cooled to room temperature, obtains the lithium cell cathode material of organic lithium salt prelithiation.
Using the lithium cell cathode material of the organic lithium salt prelithiation of preparation as lithium ion battery negative material, it is carried out
Charge and discharge and cycle performance test, test method is referring to embodiment 1.
Embodiment 6
The lithium cell cathode material of organic lithium salt prelithiation is prepared with the following method：
A, the preparation of covering material：In inert gas argon gas atmosphere, by organising for lithium source lithium metal and hydroxyl and itrile group
Object 3 is closed, 4- dihydroxybenzonitrile mixings are heated to 210 DEG C of reaction 6h, replace the hydrogen atom of hydroxyl to be formed by substitution reaction
Li-O keys, obtain covering material；The molar ratio of the hydroxyl in lithium and organic compound in lithium source is 0.2:1；Wherein, described 3,
4- dihydroxybenzonitriles are prepared with the following method：Using -4 hydroxy benzaldehyde of 3- methoxyl groups as raw material, replaced by hydroxyl anti-
3,4- 4-dihydroxy benzaldehydes should be synthesized, are heated to 40 DEG C in water later, hydroxylamine hydrochloride and sodium acetate is added, is warming up to 80 DEG C and stirs
2h is mixed, is extracted using methyl tertiary butyl ether(MTBE) after being cooled to room temperature, by obtaining 3,4- dihydroxy benzenes first after washing, drying, drying
Crude product is dissolved in chloroform by oxime crude product, is cooled to 0 DEG C, and the chloroformic solution of diethyl phosphorous acyl chlorides is added dropwise, is warmed to room temperature removing later
Chloroform and residue wash drying, are purified finally by ethyl acetate and obtain 3,4- dihydroxybenzonitriles.
B, coating modification：Covering material is heated and is melted, 20% that covering material addition is negative material weight is then pressed
Negative material is added in covering material, the negative material is carbon-based material；With the rotating speed of 2000r/min, 30min is mixed, from
It so is cooled to room temperature, obtains the lithium cell cathode material of organic lithium salt prelithiation.
Using the lithium cell cathode material of the organic lithium salt prelithiation of preparation as lithium ion battery negative material, it is carried out
Charge and discharge and cycle performance test, test method is referring to embodiment 1.
Comparative example 1
The lithium cell cathode material of organic lithium salt prelithiation is prepared with the following method：
A, the preparation of covering material：In inert gas argon gas atmosphere, by organising for lithium source lithium metal and hydroxyl and itrile group
Object 3 is closed, 4- dihydroxybenzonitrile mixings are heated to 210 DEG C of reaction 6h, replace the hydrogen atom of hydroxyl to be formed by substitution reaction
Li-O keys, obtain covering material；The molar ratio of the hydroxyl in lithium and organic compound in lithium source is 0.2:1；Wherein, described 3,
4- dihydroxybenzonitriles are prepared with the following method：Using -4 hydroxy benzaldehyde of 3- methoxyl groups as raw material, replaced by hydroxyl anti-
3,4- 4-dihydroxy benzaldehydes should be synthesized, are heated to 40 DEG C in water later, hydroxylamine hydrochloride and sodium acetate is added, is warming up to 80 DEG C and stirs
2h is mixed, is extracted using methyl tertiary butyl ether(MTBE) after being cooled to room temperature, by obtaining 3,4- dihydroxy benzenes first after washing, drying, drying
Crude product is dissolved in chloroform by oxime crude product, is cooled to 0 DEG C, and the chloroformic solution of diethyl phosphorous acyl chlorides is added dropwise, is warmed to room temperature removing later
Chloroform and residue wash drying, are purified finally by ethyl acetate and obtain 3,4- dihydroxybenzonitriles.
B, coating modification：Covering material is heated and is melted, 2% that covering material addition is negative material weight is then pressed
Negative material is added in covering material, the negative material is carbon-based material；With the rotating speed of 2000r/min, 30min is mixed, from
It so is cooled to room temperature, obtains the lithium cell cathode material of organic lithium salt prelithiation.
Using the lithium cell cathode material of the organic lithium salt prelithiation of preparation as lithium ion battery negative material, it is carried out
Charge and discharge and cycle performance test, test method is referring to embodiment 1.The lithium cell cathode material of the organic lithium salt prelithiation exists
Charging and discharging capacity and coulombic efficiency is shown in Table 1 for the first time under 0.1C.
Table 1
| Number | Capacity retention ratio after 0.1C500 cycle（%） | Coulombic efficiency for the first time（%） |
| Embodiment 1 | 75.4 | 92.1 |
| Embodiment 2 | 74.1 | 92.5 |
| Embodiment 3 | 78.7 | 93.4 |
| Embodiment 4 | 76.8 | 93.1 |
| Embodiment 5 | 75.9 | 94.5 |
| Embodiment 6 | 70.7 | 95.8 |
| Comparative example 1 | 51.5 | 80.4 |
Claims (8)
1. a kind of preparation method of the lithium cell cathode material of organic lithium salt prelithiation, which is characterized in that include the following steps：
A, the preparation of covering material：In an inert atmosphere, it by the organic compound mixing of lithium source and hydroxyl and itrile group, is heated to
160~250 DEG C of 4~8h of reaction replace the hydrogen atom of hydroxyl to form Li-O keys, obtain covering material by substitution reaction；It is described
Organic compound is the aromatic compound containing hydroxyl and mononitrile base simultaneously；And the hydroxyl in the lithium and organic compound in lithium source
The molar ratio of base is 1~2:1；
B, coating modification：Covering material is heated and is melted, 5~40% that covering material addition is negative material weight are then pressed
Negative material is added in covering material, with the rotating speed of 800~5000r/min, 10~50min is mixed, naturally cools to room temperature, obtain
To the lithium cell cathode material of organic lithium salt prelithiation.
2. the preparation method of the lithium cell cathode material of organic lithium salt prelithiation according to claim 1, it is characterised in that：
In a steps, the organic compound is 3,4- dihydroxybenzonitriles.
3. the preparation method of the lithium cell cathode material of organic lithium salt prelithiation according to claim 1, it is characterised in that：
The 3,4- dihydroxybenzonitriles are prepared with the following method：Using -4 hydroxy benzaldehyde of 3- methoxyl groups as raw material, pass through hydroxyl
Substitution reaction synthesizes 3,4- 4-dihydroxy benzaldehydes, is heated to 40 DEG C in water later, and hydroxylamine hydrochloride and sodium acetate is added, is warming up to
80 DEG C of stirring 2h, are extracted after being cooled to room temperature using methyl tertiary butyl ether(MTBE), by obtaining 3,4- dihydroxies after washing, drying, drying
Base benzene first oxime crude product, is dissolved in chloroform by crude product, is cooled to 0 DEG C, and the chloroformic solution of diethyl phosphorous acyl chlorides is added dropwise, rises to room later
Temperature removes chloroform and residue, washs drying, is purified finally by ethyl acetate and obtains 3,4- dihydroxybenzonitriles.
4. the preparation method of the lithium cell cathode material of organic lithium salt prelithiation according to claim 1, it is characterised in that：
In a steps, the lithium source is lithium metal.
5. the preparation method of the lithium cell cathode material of organic lithium salt prelithiation according to claim 1, it is characterised in that：
In a steps, the molar ratio of the hydroxyl in lithium and organic compound in lithium source is 1.2:1.
6. the preparation method of the lithium cell cathode material of organic lithium salt prelithiation according to claim 1, it is characterised in that：
In a steps, it is heated to 210 DEG C of reaction 6h.
7. the preparation method of the lithium cell cathode material of organic lithium salt prelithiation according to claim 1, it is characterised in that：
In b step, the negative material is carbon-based material or silica-base material.
8. a kind of lithium cell cathode material of organic lithium salt prelithiation, it is characterised in that：Using any one of claim 1~7 institute
The lithium cell cathode material for the organic lithium salt prelithiation that the method for stating is prepared.
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| CN109585922A (en) * | 2018-12-06 | 2019-04-05 | 清远佳致新材料研究院有限公司 | Application and high-voltage lithium ion batteries of the compound of hydroxyl in high-voltage lithium ion batteries |
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