CN107681136A - A kind of nickel phosphorus oxygen composite lithium ion battery cathode material and preparation method thereof and its negative electrode of lithium ion battery being prepared - Google Patents
A kind of nickel phosphorus oxygen composite lithium ion battery cathode material and preparation method thereof and its negative electrode of lithium ion battery being prepared Download PDFInfo
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of nickel phosphorus oxygen composite lithium ion battery cathode material and preparation method thereof and its negative electrode of lithium ion battery being prepared.The preparation method comprises the following steps：Choline Chloride and ethylene glycol are mixed, heating, stirring obtain eutectic solvent；Add cationic surfactant, after ultrasonic dissolution, sequentially add Nickelous nitrate hexahydrate and sodium dihydrogen phosphate, ultrasonic dissolution, obtain reaction precursor liquid solution；Reaction precursor liquid solution is heated to reflux, can obtain the spherical lithium ion battery negative material of nickel phosphorus oxygen micron after cleaned, dry, its main component is Ni, Ni3P, NiO, and particle carries out being self-assembled into the large scale micro-sphere material that particle diameter is 0.1~0.2 μm during preparation.It has excellent chemical property.
Description
Technical field
The present invention relates to lithium ion battery cell Material Field, and in particular to a kind of nickel-phosphor-oxygen composite lithium ion cell is born
Pole material and preparation method thereof and its negative electrode of lithium ion battery being prepared.
Background technology
With the fast development of power lithium-ion battery, lithium ion battery cathode material is widely paid close attention to.Pass
The capacity of the cathode material for lithium-ion power battery of system is low, cycle performance and high rate performance is poor and there is safety to ask
Topic.
The carbon materials such as graphite, hard carbon, soft carbon are the main negative materials of current commercial Li-ion battery.But these carbon materials
The storage lithium poor-performing of material, result in relatively low charge/discharge capacity, largely, limit the property of lithium-ion-power cell
Energy.Transition metal phosphide receives extensive concern due to its relatively low polarizability and higher cyclical stability.Wherein nanometer
Microstructure of the Ni-P alloys of structure based on its controlled dimensions and size, shows excellent electromagnetism, electronics and optics
Performance, it is a kind of very promising lithium ion battery negative material.
Metal phosphide can be from solvent thermal process, the reduction process of transition metal phosphide, metal or metal oxide
Parkerizing process, the decomposable process of metal complex, the precipitation process of solution, and the reaction of organometallic reagent and hydrogen phosphide
Process obtains.The Ni-P alloys of nanostructured generally require template to assist the formation of its nanostructured, and conventional template is Al/
Al2O3Template.The synthesis step of the method is relatively complicated, and preparation technology is complex, is unsuitable for industrialized production.In addition, to pass
When the wet chemistry method of system prepares Ni-P alloys, higher temperature is generally required, reaction dissolvent is generally the aqueous solution, also causes reaction
It could carry out under high pressure.The method not only complex steps, and harsh reaction condition has the high requirement of comparison to equipment,
There is also certain potential safety hazard simultaneously.
Publication No. CN 104190921A Chinese patent discloses a kind of Au/Ni12P5The system of core-shell structure nanometer particle
Preparation Method, this method is using Au-Ni dumbbell structures as presoma, and after adding triphenylphosphine pyroreaction, Au/Ni is made12P5Nucleocapsid
Material.The material is a kind of nano material of the metal-semiconductor core shell structure with single crystal semiconductor shell, is possessed well
Stability and capacitive property, but its preparation process is cumbersome, it is with high costs using Au nano materials as presoma, it is unfavorable for scale
Production.
Because ionic liquid possesses higher heat endurance and relatively low vapour pressure, it is (big that high temperature can be carried out at ambient pressure
In 100 DEG C) reaction.Ionic liquid can both be used as reaction dissolvent, can be used as template again, eliminate between solvent and template
Influence each other, thus be widely used in the building-up process of nano material.The A of Publication No. CN 102623679 Chinese patent is public
Opened a kind of preparation method of gentle Ni-P alloy materials, in the method, using a kind of eutectic solvent as reaction dissolvent and
Template, using Nickelous nitrate hexahydrate and ammonium dihydrogen phosphate as nickel source and phosphorus source, a kind of Ni-P alloy materials of core shell structure are obtained
Material.The material shows preferable chemical property, but the tap density of the nano material is relatively low, is unfavorable for the hair of its performance
Wave.
The content of the invention
In order to solve the above technical problems, the invention provides a kind of nickel-phosphor-oxygen composite lithium ion battery cathode material and its
Preparation method and its negative electrode of lithium ion battery being prepared.
The technical scheme that the present invention takes is：
A kind of preparation method of nickel-phosphor-oxygen composite lithium ion battery cathode material, the preparation method include following step
Suddenly：
(1) Choline Chloride and ethylene glycol are mixed, heating, stirring obtain eutectic solvent；
(2) cationic surfactant is added in the eutectic solvent obtained to step (1), after ultrasonic dissolution, successively
Nickelous nitrate hexahydrate and sodium dihydrogen phosphate, ultrasonic dissolution are added, obtains reaction precursor liquid solution；
(3) reaction precursor liquid solution is heated to reflux, nickel-phosphor-oxygen compound lithium ion electricity is can obtain after cleaned, dry
Pond negative material.
The cationic surfactant is DTAB.
Thing between the Choline Chloride, ethylene glycol, cationic surfactant, Nickelous nitrate hexahydrate, sodium dihydrogen phosphate
The ratio between amount of matter is 1：0.5~4：0.05~0.4：0.01~1.2：0.01~1.2；Preferably 1：1.5~2.5：0.09~
0.25：0.014~0.025：0.012~0.05.
The ratio between amount of material of the Nickelous nitrate hexahydrate and sodium dihydrogen phosphate is preferably 1:2~10.
In the step (1), the temperature and time of heating is respectively 60~120 DEG C, 0.5~2h.
In the step (2), the time of ultrasonic dissolution is 0.5~3 hour.
In the step (3), the temperature being heated to reflux is 100~350 DEG C, and the time is 1~5h.
In the step (3), clean and wash and wash for alternately alcohol, described alcohol is preferably ethanol；Dry is 40
~80 DEG C of dry 3~13h.
Present invention also offers a kind of nickel-phosphor-oxygen composite lithium ion cell being prepared according to above-mentioned preparation method to bear
Pole material, Ni, Ni in the composition of the material3The mol ratio of P and NiO threes is 1：1~3：0.5~2 composition, its particle diameter are
0.1~0.2 μm.
Present invention also offers a kind of preparation method of negative electrode of lithium ion battery, the preparation method comprises the following steps：
A. weighed after copper foil is cleaned；
B. 80~200mg/ml polyvinylidene fluoride solution is prepared using 1-METHYLPYRROLIDONE as solvent, will be according to above-mentioned
The nickel-phosphor that preparation method is prepared-oxygen composite lithium ion battery cathode material, carbon black, polyvinylidene fluoride solution are by quality
Than for 90~95:1~3:2~8 mixing, grinding make it well mixed, obtain electrode slurry；
C. electrode slurry is spread evenly across into step a to obtain on copper foil, be dried in vacuo, electrode slice is made；
D. copper foil electrode slice obtained with step a encases up and down, is put in mould, compressing, then in argon gas
Button-shaped half-cell is assembled in glove box.
In the step c, vacuum drying temperature is 100~120 DEG C.
In the step d, compressing pressure is 8~12Mpa.
In the preparation method of nickel-phosphor provided by the invention-oxygen composite lithium ion battery cathode material, with Choline Chloride and second
It is solvent that glycol, which dissolves by heating the eutectic solvent formed afterwards, and DTAB is soft template, with six hydrations
Nickel nitrate and sodium dihydrogen phosphate are nickel source and phosphorus source, are flowed back by constant-pressure and high-temperature, allow particle to carry out self assembly, and then obtain one kind
Particle diameter is the Ni-P-O micro-sphere materials of 0.1~0.2 μm of large scale core shell structure.
The generation of core shell structure depends on cationic surfactant in the present invention and the collaboration of eutectic solvent is made
With the different choice of nickel source also results in different core shell structures.Nitrate anion in Nickelous nitrate hexahydrate can disturb chlorine
Change the stability of the Chloride-ion System in choline, break the balance system of chlorion.Ionic radius of the nitrate anion than chlorion
Big, mobility in a solvent is relatively low, can increase Ni2+With the H of Ni-P particle surfaces2PO2-Contact probability, accelerate into
Core speed, ultimately form the spherical composite construction of micron.In addition, biphosphate sodium raw materials of the present invention are with higher
Heat endurance, participate in reacting more stable in building-up process, make the preparation process of experiment there is controllability.
Compared with prior art, the present invention possesses advantages below：
1. the preparation process of nickel-phosphor-oxygen composite lithium ion battery cathode material is simple, mild condition is controllable；It is used
Raw material is conventional chemical substance, and cheap, and the yield for the negative material being prepared by these raw materials is higher；
2. nickel-phosphor-oxygen composite lithium ion battery cathode material is the core shell structure that particle diameter is 0.1~0.2 μm, the thickness of shell
For 3nm；
3. nickel-phosphor-oxygen composite lithium ion battery cathode material is mainly by Ni, Ni3P, NiO are formed, and its molar ratio is 1:1
~3:0.2~1；
Brief description of the drawings
Fig. 1 is the XRD test charts of nickel-phosphor-oxygen composite lithium ion battery cathode material in embodiment 1；
Fig. 2 is nickel-phosphor-oxygen composite lithium ion battery cathode material scanning electron microscope (SEM) photograph in embodiment 1；
Fig. 3 is nickel-phosphor-oxygen composite lithium ion battery cathode material transmission electron microscope picture in embodiment 2；
Fig. 4 is the high-resolution-ration transmission electric-lens figure of nickel-phosphor-oxygen composite lithium ion battery cathode material in embodiment 3；
Fig. 5 be using in embodiment 4 nickel-phosphor-oxygen composite lithium ion battery cathode material be prepared as raw material it is button-shaped
The charging and discharging curve figure of half-cell.
Embodiment
Embodiment 1
A kind of preparation method of nickel-phosphor-oxygen composite lithium ion battery cathode material, comprises the following steps：
(1) 50g Choline Chlorides and 44.6g ethylene glycol are added in 50ml three-necked flask, stirred 1 hour at 80 DEG C,
Obtain eutectic solvent；
(2) add 22g DTABs, ultrasonic dissolution, then add 1.45g Nickelous nitrate hexahydrates with
1.06g sodium dihydrogen phosphates, ultrasound make its dissolving in 1 hour, obtain reaction precursor liquid solution；
(3) reaction precursor liquid solution is flowed back 3 hours at 150 DEG C, when color from it is light green be changed into black when, stop back
Stream, is cooled to room temperature, and be centrifuged at a high speed sediment, and alternating deionized water and alcohol flushing are three times, finally, by sediment
It is put into 60 DEG C of drying box, dries 6 hours, it is nickel-phosphor-oxygen composite lithium ion battery cathode material to obtain black solid powder
Material, tested after material progress high-temperature crystallization, then through XRD, test result is as shown in Figure 1.Can by preliminary quantitative analysis
Know, its composition is mainly by Ni, Ni3P, NiO is 1 in molar ratio:2.5:2 compositions.
The ESEM that the present embodiment prepares nickel-phosphor-oxygen composite lithium ion battery cathode material is as shown in Figure 2, it is known that, its
For sphere material of the particle size between 0.1~0.2 μm.
The nickel-phosphor obtained using the present embodiment-oxygen composite lithium ion battery cathode material prepares lithium-ion electric as one of raw material
Pond negative pole, is concretely comprised the following steps：
A. copper foil is placed in ultrasonic 3-5min in ethanol, copper foil is then placed in ultrasonic 3-5min in acetone soln, then
Cleaned with deionized water, dry and weigh；
B. 80~200mg/ml polyvinylidene fluoride solution is prepared using 1-METHYLPYRROLIDONE as solvent, will be according to right
It is required that nickel-phosphor-oxygen composite lithium ion battery cathode material, carbon black, the polyvinylidene fluoride that the preparation method in 1 is prepared are molten
Liquid is 90 in mass ratio:2:8 mixing, grinding make it well mixed, obtain electrode slurry；
C. electrode slurry is spread evenly across into step a to obtain on copper foil, 100~120 DEG C of vacuum drying, electrode slice is made；
D. copper foil electrode slice obtained with step a encases up and down, is put in mould, is suppressed under 8~12Mpa pressure
Shaping, then assembles button-shaped half-cell in the glove box of argon gas.
Charge-discharge test is carried out to it, charging/discharging voltage scope is 0.02~3.0V, and test environment temperature is room temperature 25
DEG C, charging and discharging currents 50mA/g, through 50 loop tests, its battery capacity maintains more than 300mAh/g.
Embodiment 2
A kind of preparation method of nickel-phosphor-oxygen composite lithium ion battery cathode material, comprises the following steps：
(1) 50g Choline Chlorides and 44.6g ethylene glycol are added in 50ml three-necked flask, stirred 1 hour at 100 DEG C,
Obtain eutectic solvent；
(2) add 22g DTABs, ultrasonic dissolution, then add 1.45g Nickelous nitrate hexahydrates with
0.53g sodium dihydrogen phosphates, ultrasound make its dissolving in 0.5 hour, obtain reaction precursor liquid solution；
(3) reaction precursor liquid solution is flowed back 3 hours at 120 DEG C, when color from it is light green be changed into black when, stop back
Stream, is cooled to room temperature, and be centrifuged at a high speed sediment, and alternating deionized water and alcohol flushing are three times；Finally, by sediment
It is put into 60 DEG C of drying box, dries 3 hours, it is nickel-phosphor-oxygen composite lithium ion battery cathode material to obtain black solid powder
Material, through XRD, its composition is mainly by Ni, Ni3P, NiO is 1 in molar ratio:1.5:1.2 composition.
Nickel-phosphor manufactured in the present embodiment-oxygen composite lithium ion battery cathode material, its transmission electron microscope is as shown in figure 3, can
Know, resulting nickel-phosphor-oxygen composite lithium ion battery cathode material is core shell structure, particle size 0.1~0.2 μm it
Between.
The nickel-phosphor obtained using the present embodiment-oxygen composite lithium ion battery cathode material prepares lithium-ion electric as one of raw material
Pond negative pole, is concretely comprised the following steps：
A. copper foil is placed in ultrasonic 3-5min in ethanol, copper foil is then placed in ultrasonic 3-5min in acetone soln, then
Cleaned with deionized water, dry and weigh；
B. 80~200mg/ml polyvinylidene fluoride solution is prepared using 1-METHYLPYRROLIDONE as solvent, will be according to right
It is required that nickel-phosphor-oxygen composite lithium ion battery cathode material, carbon black, the polyvinylidene fluoride that the preparation method in 1 is prepared are molten
Liquid is 92 in mass ratio:1:7 mixing, grinding make it well mixed, obtain electrode slurry；
C. electrode slurry is spread evenly across into step a to obtain on copper foil, 100~120 DEG C of vacuum drying, electrode slice is made；
D. copper foil electrode slice obtained with step a encases up and down, is put in mould, is suppressed under 8~12Mpa pressure
Shaping, then assembles button-shaped half-cell in the glove box of argon gas.
Charge-discharge test is carried out to it, charging/discharging voltage scope is 0.02~3.0V, and test environment temperature is room temperature 25
DEG C, charging and discharging currents 50mA/g, through 50 loop tests, its battery capacity maintains more than 310mAh/g.
Embodiment 3
A kind of preparation method of nickel-phosphor-oxygen composite lithium ion battery cathode material, comprises the following steps：
(1) 50g Choline Chlorides and 44.6g ethylene glycol are added in 50ml three-necked flask, stirred 1 hour at 80 DEG C,
Obtain eutectic solvent；
(2) add 11g DTABs, ultrasonic dissolution, then add 2.18g Nickelous nitrate hexahydrates with
1.06g sodium dihydrogen phosphates, ultrasound make its dissolving in 1 hour, obtain reaction precursor liquid solution；
(3) reaction precursor liquid solution is flowed back 1.5 hours at 100 DEG C, when color from it is light green be changed into black when, stop back
Stream, is cooled to room temperature, and be centrifuged at a high speed sediment, and alternating deionized water and alcohol flushing are three times, and sediment is put into
In 60 DEG C of drying box, dry 6 hours, it is nickel-phosphor-oxygen composite lithium ion battery cathode material to obtain black solid powder,
Through XRD, its composition is mainly by Ni, Ni3P, NiO is 1 in molar ratio:2:1.5 composition.
Nickel-phosphor manufactured in the present embodiment-oxygen composite lithium ion battery cathode material, its high-resolution-ration transmission electric-lens figure such as Fig. 4
It is shown, it is known that, resulting nickel-phosphor-oxygen composite lithium ion battery cathode material is core shell structure, and the thickness of shell is 3nm.
The nickel-phosphor obtained using the present embodiment-oxygen composite lithium ion battery cathode material prepares lithium-ion electric as one of raw material
Pond negative pole, is concretely comprised the following steps：
A. copper foil is placed in ultrasonic 3-5min in ethanol, copper foil is then placed in ultrasonic 3-5min in acetone soln, then
Cleaned with deionized water, dry and weigh；
B. 80~200mg/ml polyvinylidene fluoride solution is prepared using 1-METHYLPYRROLIDONE as solvent, will be according to right
It is required that nickel-phosphor-oxygen composite lithium ion battery cathode material, carbon black, the polyvinylidene fluoride that the preparation method in 1 is prepared are molten
Liquid is 93 in mass ratio:2:5 mixing, grinding make it well mixed, obtain electrode slurry；
C. electrode slurry is spread evenly across into step a to obtain on copper foil, 100~120 DEG C of vacuum drying, electrode slice is made；
D. copper foil electrode slice obtained with step a encases up and down, is put in mould, is suppressed under 8~12Mpa pressure
Shaping, then assembles button-shaped half-cell in the glove box of argon gas.And charge-discharge test is carried out to it.Charging/discharging voltage scope
For 0.02~3.0V, test environment temperature is 25 DEG C of room temperature, and charging and discharging currents 50mA/g, its battery capacity maintains
More than 290mAh/g.
Embodiment 4：
A kind of preparation method of nickel-phosphor-oxygen composite lithium ion battery cathode material, comprises the following steps：
(1) 50g Choline Chlorides and 44.6g ethylene glycol are added in 50ml three-necked flask, stirred 1 hour at 80 DEG C,
Obtain eutectic solvent；
(2) add 22g DTABs, ultrasonic dissolution, then add 2.18g Nickelous nitrate hexahydrates with
1.59g sodium dihydrogen phosphates, ultrasound make its dissolving in 1 hour, obtain reaction precursor liquid solution；
(3) reaction precursor liquid solution is flowed back 3 hours at 120 DEG C, when color have it is light green be changed into black when, stop back
Stream, is cooled to room temperature, and be centrifuged at a high speed sediment, and alternating deionized water and alcohol flushing are three times.Finally, by sediment
It is put into 100 DEG C of drying box, dries 8 hours, it is nickel-phosphor-oxygen composite lithium ion battery cathode to obtain black solid powder
Material, tested through XRD, its composition is mainly by Ni, Ni3P, NiO is 1 in molar ratio:3:2 compositions.
The nickel-phosphor obtained using the present embodiment-oxygen composite lithium ion battery cathode material prepares lithium-ion electric as one of raw material
Pond negative pole, is concretely comprised the following steps：
A. copper foil is placed in ultrasonic 3-5min in ethanol, copper foil is then placed in ultrasonic 3-5min in acetone soln, then
Cleaned with deionized water, dry and weigh；
B. 80~200mg/ml polyvinylidene fluoride solution is prepared using 1-METHYLPYRROLIDONE as solvent, will be according to right
It is required that nickel-phosphor-oxygen composite lithium ion battery cathode material, carbon black, the polyvinylidene fluoride that the preparation method in 1 is prepared are molten
Liquid is 95 in mass ratio:2:3 mixing, grinding make it well mixed, obtain electrode slurry；
C. electrode slurry is spread evenly across into step a to obtain on copper foil, 100~120 DEG C of vacuum drying, electrode slice is made；
D. copper foil electrode slice obtained with step a encases up and down, is put in mould, is suppressed under 8~12Mpa pressure
Shaping, then assembles button-shaped half-cell in the glove box of argon gas.And charge-discharge test is carried out to it.Charging/discharging voltage scope
For 0.02~3.0V, test environment temperature is 25 DEG C, charging and discharging currents 50mA/g of room temperature, and test result is as shown in figure 5, from figure
5 through 50 loop tests, its battery capacity it can be seen that maintain more than 290mAh/g.
It is above-mentioned to a kind of nickel-phosphor-oxygen composite lithium ion battery cathode material and preparation method thereof and its to be made with reference to embodiment
The detailed description that standby obtained negative electrode of lithium ion battery is carried out, be it is illustrative rather than limited, can be according to limited model
Enclose and include several embodiments, therefore changing and modifications in the case where not departing from present general inventive concept, guarantor of the invention should be belonged to
Within the scope of shield.
Claims (10)
- A kind of 1. preparation method of nickel-phosphor-oxygen composite lithium ion battery cathode material, it is characterised in that the preparation method bag Include following steps：(1) Choline Chloride and ethylene glycol are mixed, heating, stirring obtain eutectic solvent；(2) add cationic surfactant in the eutectic solvent obtained to step (1), after ultrasonic dissolution, sequentially add Nickelous nitrate hexahydrate and sodium dihydrogen phosphate, ultrasonic dissolution, obtain reaction precursor liquid solution；(3) reaction precursor liquid solution is heated to reflux, can obtain nickel-phosphor-oxygen composite lithium ion cell after cleaned, dry bears Pole material.
- 2. preparation method according to claim 1, it is characterised in that the cationic surfactant is dodecyl three Methyl bromide ammonium.
- 3. preparation method according to claim 1, it is characterised in that the Choline Chloride, ethylene glycol, cationic surface are lived Property agent, Nickelous nitrate hexahydrate, the ratio between the amount of material between sodium dihydrogen phosphate be 1：0.5~4：0.05~0.4：0.01~1.2： 0.01~1.2.
- 4. preparation method according to claim 3, it is characterised in that the Choline Chloride, ethylene glycol, cationic surface are lived Property agent, Nickelous nitrate hexahydrate, the ratio between the amount of material between sodium dihydrogen phosphate be 1：1.5~2.5：0.09~0.25：0.014~ 0.025：0.012~0.05.
- 5. according to the preparation method described in claim 1 or 3 or 4, it is characterised in that the Nickelous nitrate hexahydrate and biphosphate The ratio between amount of material of sodium is 1:2~10.
- 6. preparation method according to claim 1, it is characterised in that in the step (1), the temperature and time point of heating Wei not 60~120 DEG C, 0.5~2h.
- 7. preparation method according to claim 1 or 5, it is characterised in that in the step (3), the temperature that is heated to reflux For 100~350 DEG C, the time is 1~5h.
- A kind of 8. nickel-phosphor that preparation method according to claim 1 is prepared-oxygen composite lithium ion battery cathode material Material, it is characterised in that Ni, Ni in the composition of the material3The mol ratio of P and NiO threes is 1：1~3：0.5~2 composition, its Particle diameter is 0.1~0.2 μm.
- 9. a kind of preparation method of negative electrode of lithium ion battery, it is characterised in that the preparation method comprises the following steps：A. weighed after copper foil is cleaned；B. 80~200mg/ml polyvinylidene fluoride solution is prepared using 1-METHYLPYRROLIDONE as solvent, will be according to claim The nickel-phosphor that preparation method in 1 is prepared-oxygen composite lithium ion battery cathode material, carbon black, polyvinylidene fluoride solution by Mass ratio is 90~95:1~3:2~8 mixing, grinding make it well mixed, obtain electrode slurry；C. electrode slurry is spread evenly across into step a to obtain on copper foil, be dried in vacuo, electrode slice is made；D. copper foil electrode slice obtained with step a encases up and down, is put in mould, compressing, then in the gloves of argon gas Button half-cell is assembled in case.
- 10. preparation method according to claim 8, it is characterised in that in the step d, compressing pressure be 8~ 12Mpa。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526939A (en) * | 2019-08-28 | 2019-12-03 | 衢州市求是科技联合会 | Alkoxy oligomerisation phosphoric acid ethylene ester metal salt and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050173254A1 (en) * | 2004-02-05 | 2005-08-11 | George Bokisa | Nickel cobalt boron ternary alloys |
| CN101237038A (en) * | 2008-01-21 | 2008-08-06 | 华南师范大学 | A tin nickel alloy negative material of lithium ion battery and its making method |
| CN102623679A (en) * | 2012-03-27 | 2012-08-01 | 浙江大学 | Preparation method of Ni-P alloy lithium ion battery cathode material of core-shell structure |
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2017
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Patent Citations (3)
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|---|---|---|---|---|
| US20050173254A1 (en) * | 2004-02-05 | 2005-08-11 | George Bokisa | Nickel cobalt boron ternary alloys |
| CN101237038A (en) * | 2008-01-21 | 2008-08-06 | 华南师范大学 | A tin nickel alloy negative material of lithium ion battery and its making method |
| CN102623679A (en) * | 2012-03-27 | 2012-08-01 | 浙江大学 | Preparation method of Ni-P alloy lithium ion battery cathode material of core-shell structure |
Non-Patent Citations (1)
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| 董栋等: "化学镀Ni-P及Ni-P-SiO2复合镀层的制备及性能研究", 《2009年全国青年摩擦学学术会议论文集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526939A (en) * | 2019-08-28 | 2019-12-03 | 衢州市求是科技联合会 | Alkoxy oligomerisation phosphoric acid ethylene ester metal salt and its preparation method and application |
| CN110526939B (en) * | 2019-08-28 | 2022-02-15 | 衢州市求是科技联合会 | Alkoxy oligopolyethylene phosphate metal salt and preparation method and application thereof |
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