CN101237038A - A tin nickel alloy negative material of lithium ion battery and its making method - Google Patents
A tin nickel alloy negative material of lithium ion battery and its making method Download PDFInfo
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- CN101237038A CN101237038A CNA2008100259241A CN200810025924A CN101237038A CN 101237038 A CN101237038 A CN 101237038A CN A2008100259241 A CNA2008100259241 A CN A2008100259241A CN 200810025924 A CN200810025924 A CN 200810025924A CN 101237038 A CN101237038 A CN 101237038A
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- nickel alloy
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- ion battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a Li-ion battery tin-nickel alloy cathode material. The preparation method comprises the following steps of: firstly, preparing plating solution, adding the plating solution into a plating bath, plating by connecting a tin sheet with a nickel sheet together as the anode and clutch gold as the cathode, cutting the plated clutch gold into sheets after washing and drying to obtain the Li-ion battery tin-nickel alloy cathode material. The method is simple and easy to operate, provides conditions for industrialized production and is of notable practical value and economic benefit. The Li-ion battery tin-nickel alloy cathode material prepared and obtained has no active nickel of intercalation/deintercalation Lithium freed from the tin-nickel alloy cathode material during and charging and discharging and is dispersed evenly on the tine-nickel alloy formed after Lithium intercalation, avoiding agglomeration of big tin block during Lithium deintercalation.
Description
Technical field
The invention belongs to the lithium ion battery field, particularly a kind of tin nickel alloy negative material of lithium ion battery and preparation method thereof.
Background technology
At present, lithium rechargeable battery has become the important energy source of portable set.Material with carbon element is the negative material of present business-like lithium ion battery, and its theoretical capacity is 372mAhg
-1, be difficult to satisfy the miniaturization development of present various electronic equipments and electric automobile widespread demand to the large-capacity high-power chemical power source.Therefore more and more active to the research of the novel alloy negative pole of replaceable existing carbon negative pole.
Lithium can reversibly form alloy with most of metals (Si, Sn, Sb etc.).These metals can be used as lithium ion battery negative material, and what wherein study morely is stannum alloy cathode material.(theoretical capacity is 990mAhg to the lithium storage content of tin base cathode material than material with carbon element height
-1).Find in the research that lithium takes off in the process in the embedding of tin particulate, caused the expansion and the contraction of tin particulate volume, when lithium embedded, its volume was inflatable 259%, this expansion and shrink and cause the collapse of tin clustering architecture easily, thus storage lithium capacity is reduced rapidly.Metallic tin has been subjected to considerable restraint as the application of negative material.Therefore present many researchers are devoted to the modification and the optimal design of this high storage lithium performance materials, and in order to overcome huge bulk effect, the intermetallic compound of " active/nonactive " is subjected to extensive concern as the thought of negative material.As adopt superfine alloy and activity/nonactive composite alloy system, mainly comprise Sn/Cu, Sn/Sb or the like, most molten alloy method, the machine-alloyings etc. of adopting of above-mentioned system make alloy powder, the method that adopts the polytetrafluoroethylene bonding to apply then prepares electrode, yet the intermiscibility of metal dust and binding agent is very poor, the often easy powder of detached of the electrode active material that applies causes electrochemical stability very poor.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of tin nickel alloy negative material of lithium ion battery is provided.
Another object of the present invention is to provide a kind of preparation method of tin nickel alloy negative material of lithium ion battery.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of tin nickel alloy negative material of lithium ion battery comprises the steps:
(1) the preparation electroplate liquid makes the addition of each component in every liter of electroplate liquid as follows: SnCl2H
2O 0.10～0.36mol, NiCl6H
2O 0.09～0.35mol, K
4P
2O
73H
2O 0.5～1.5mol, glycine (glycine) 0.1～0.2mol; Add NH then
4It is standby that OH regulates pH to 7.5～8.5;
(2) electroplate liquid for preparing in the step (1) being added in the electroplating bath, tin sheet and nickel sheet are linked together as anode, is negative electrode with the copper foil, is 0.05～0.15Adm at 30～45 ℃, current density
-2Condition under electroplated 5～10 minutes;
(3) cut a sheet after the copper foil clean dry after will electroplating and promptly make described tin nickel alloy negative material of lithium ion battery.
Sn in the electroplate liquid of being prepared in the described step (1)
2+And Ni
2+Mol ratio be 0.25～4: 1.
Sn in the electroplate liquid of being prepared in the preferred steps (1)
2+And Ni
2+Total concentration be K
4P
2O
73H
21/2 of O concentration.
Copper foil adopts single face to electroplate in the preferred steps (2).
Be to be 0.05～0.15Adm in the preferred steps (2) at 30～45 ℃, current density
-2, the auxiliary stirring condition of ultrasonic wave electroplated 5～10 minutes down.
The preferred dry vacuumize that is.
By containing Ni in the said method lithium ion cell prepared tin nickel alloy negative material
3Sn
4Or the metastable phasing of NiSn, tin-nickel alloy is as active material, and free nickel rises and disperses and electric action.
The present invention utilizes inductance coupled plasma element emission spectrum instrument (ICP-AES) to measure the quality of Sn and Ni in the preparation-obtained tin nickel alloy negative material of lithium ion battery, thereby calculates the tin content of different-alloy.
The present invention has following advantage and beneficial effect with respect to prior art:
(1) tin nickel alloy negative material of lithium ion battery of the present invention's preparation, in the charge and discharge cycles process, do not have the nickel of doff lithium activity from tin-nickel alloy, to dissociate out, and the tin lithium alloy that the back of will discharging generates evenly disperses, prevented to take off the reunion of bulk tin in the lithium process.
(2) the present invention has adopted the ultrasonic wave supplementary means in electroplating preparation process, makes tin-nickel coating eliminate residual mechanical stresses, has effectively avoided the bulk effect of tin-nickel alloy when doff lithium to a certain extent, has improved the cycle performance of electrode.
(3) technology of the present invention is simple, and is easy and simple to handle, for suitability for industrialized production provides condition, has significant practical value and economic benefit.
Description of drawings
Fig. 1 is the XRD figure spectrum of the tin nickel alloy negative material of lithium ion battery and the pure nickel of the prepared different tin content of the present invention;
Fig. 2 is the embodiment of the invention 1～5 and the prepared product of the comparative example discharge capacity attenuation curve during as work electrode.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but the working of an invention mode is not limited thereto.
Embodiment 1
(1) with 0.9mol K
4P
2O
73H
2O and 0.1mol glycine are dissolved in a certain amount of deionized water, then with 0.10mol SnCl2H
2O, 0.35mol NiCl
26H
2O joins in the above-mentioned solution and dissolves, and adds water and is settled to 1L, adds NH at last
4OH regulates pH to 7.5.
(2) electroplate liquid for preparing in the step (1) is added in the electroplating bath, tin sheet and nickel sheet are linked together as anode, is negative electrode with lithium ion battery with negative current collector copper foil (thickness is 10 microns), copper foil is simultaneously coated the oiliness pen and ink, covering one side and realize that single face electroplates, is 0.05Adm at 45 ℃, current density
-2Electroplated 10 minutes under the condition;
(3) the copper foil flush away printing ink in acetone after will electroplating with distilled water washing 3 times, dries up under the normal temperature again, and 100 ℃ of following vacuumize 12h are the disk of diameter 10mm then with its section sheet, and weighing promptly makes the tin-nickel alloy electrode material.
Tin content in the preparation-obtained tin nickel alloy negative material of lithium ion battery is 45.2%, and the relation of Sn/Ni mol ratio is as shown in table 1 in itself and the electroplate liquid.Its XRD figure spectrum as shown in Figure 1, as can be seen from Figure 1 in this tin nickel alloy negative material of lithium ion battery mainly by Ni
3Sn
4Form.
As work electrode, the pour lithium slice conduct is to electrode with preparation-obtained tin nickel alloy negative material of lithium ion battery, and the solute of electrolyte is LiPF
6, concentration is 1molL
-1, solvent is vinyl carbonate (EC): dimethyl carbonate (DMC): the mixed solvent of Methylethyl carbonic ester (EMC)=1: 1: 1 (volume ratio), barrier film is microporous polypropylene membrane Celgard-2300, is assembled into the CR2016 button cell in Ar gas glove box (water content and oxygen content all are lower than 1ppm).Under the room temperature, in electro-chemical test work station (Solartron SI1260) system, carry out the constant current charge-discharge loop test.Charging and discharging currents density is 0.1mAcm
-2In the charge and discharge cycles process, do not have the nickel of doff lithium activity from tin-nickel alloy, to dissociate out, and the tin lithium alloy that forms behind the embedding lithium is evenly disperseed, prevented to take off the reunion of bulk tin in the lithium process.The discharge capacity attenuation curve of this tin nickel alloy negative material of lithium ion battery during as work electrode as shown in Figure 2, the about 411mAhg of initial discharge capacity as can be seen from Figure 2
-1, 30 times circulation back discharge capacity remains on 172mAhg
-1, but 7 the later capacity that circulate have bigger decay.
Embodiment 2
(1) with 0.9molK
4P
2O
73H
2O and 0.1mol glycine are dissolved in a certain amount of deionized water, then with 0.15mol SnCl2H
2O, 0.30mol NiCl
26H
2O joins in the above-mentioned solution and dissolves, and adds water and is settled to 1L, adds NH at last
4OH regulates pH to 8.
(2) electroplate liquid for preparing in the step (1) is added in the electroplating bath, tin sheet and nickel sheet are linked together as anode, is negative electrode with lithium ion battery with negative current collector copper foil (thickness is 10 microns), copper foil is simultaneously coated the oiliness pen and ink, covering one side and realize that single face electroplates, is 0.1Aam at 40 ℃, current density
-2Electroplated 10 minutes under the condition;
(3) the copper foil flush away printing ink in acetone after will electroplating with distilled water washing 2 times, dries up under the normal temperature again, and 100 ℃ of following vacuumize 12h are the disk of diameter 10mm then with its section sheet, and weighing promptly makes described tin nickel alloy negative material of lithium ion battery.
Tin content in the preparation-obtained tin nickel alloy negative material of lithium ion battery is 62.7%, and the relation of Sn/Ni mol ratio is as shown in table 1 in itself and the electroplate liquid.Its XRD figure spectrum as shown in Figure 1, as can be seen from Figure 1 in this tin nickel alloy negative material of lithium ion battery mainly by Ni
3Sn
4Form.
As work electrode, the pour lithium slice conduct is to electrode with preparation-obtained tin nickel alloy negative material of lithium ion battery, and the solute of electrolyte is LiPF
6, concentration is 1molL
-1, solvent is vinyl carbonate (EC): dimethyl carbonate (DMC): the mixed solvent of Methylethyl carbonic ester (EMC)=1: 1: 1 (volume ratio), barrier film is microporous polypropylene membrane Celgard-2300, is assembled into the CR2016 button cell in Ar gas glove box (water content and oxygen content all are lower than 1ppm).Under the room temperature, in Solartron SI1260 system, carry out the constant current charge-discharge loop test.Charging and discharging currents density is 0.1mAcm
-2In the charge and discharge cycles process, do not have the nickel of doff lithium activity from tin-nickel alloy, to dissociate out, and the tin lithium alloy that forms behind the embedding lithium is evenly disperseed, prevented to take off the reunion of bulk tin in the lithium process.The discharge capacity attenuation curve of this tin nickel alloy negative material of lithium ion battery during as work electrode as shown in Figure 2, the about 554mAhg of initial discharge capacity as can be seen from Figure 2
-1, 30 times circulation back discharge capacity remains on 276mAhg
-1, cycle performance is more stable.
Embodiment 3
(1) with 0.9mol K
4P
2O
73H
2O and 0.1mol glycine are dissolved in a certain amount of deionized water, then with 0.23mol SnCl2H
2O, 0.22mol NiCl
26H
2O joins in the above-mentioned solution and dissolves, and adds water and is settled to 1L, adds NH at last
4OH regulates pH to 8.5.
(2) electroplate liquid for preparing in the step (1) is added in the electroplating bath, tin sheet and nickel sheet are linked together as anode, is negative electrode with lithium ion battery with negative current collector copper foil (thickness is 10 microns), copper foil is simultaneously coated the oiliness pen and ink, covering one side and realize that single face electroplates, is 0.15Adm at 30 ℃, current density
-2Electroplated 5 minutes under the condition;
(3) the copper foil flush away printing ink in acetone after will electroplating with distilled water washing 2 times, dries up under the normal temperature again, and 100 ℃ of following vacuumize 12h are the disk of diameter 10mm then with its section sheet, and weighing promptly makes described tin nickel alloy negative material of lithium ion battery.
Tin content in the preparation-obtained tin nickel alloy negative material of lithium ion battery is 78.5%, and the relation of Sn/Ni mol ratio is as shown in table 1 in itself and the electroplate liquid.Its XRD figure spectrum mainly contains the metastable phasing of NiSn as shown in Figure 1 as can be seen from Figure 1 in this tin nickel alloy negative material of lithium ion battery.The discharge capacity attenuation curve of this tin nickel alloy negative material of lithium ion battery during as work electrode as shown in Figure 2, the about 761mAhg of initial discharge capacity as can be seen from Figure 2
-1, 30 times circulation back discharge capacity decays to 91mAhg
-1, capacity attenuation is very serious, and cyclical stability is poor.
Embodiment 4
Present embodiment except that following characteristics with embodiment 2: the NiCl6H that is added
2O is 0.09mol; The SnCl2H that is added
2O is 0.36mol.
Tin content in the preparation-obtained tin nickel alloy negative material of lithium ion battery is 86.1%, and the relation of Sn/Ni mol ratio is as shown in table 1 in itself and the electroplate liquid.Its XRD figure spectrum as shown in Figure 1, as can be seen from Figure 1 in this tin nickel alloy negative material of lithium ion battery mainly by Ni
3Sn
4Form.The discharge capacity attenuation curve of this tin nickel alloy negative material of lithium ion battery during as work electrode as shown in Figure 2, the about 845mAhg of initial discharge capacity as can be seen from Figure 2
-1, 30 times circulation back discharge capacity decays to 120mAhg
-1, capacity attenuation is very serious, and cyclical stability is poor.
Embodiment 5
Present embodiment except that following characteristics with embodiment 2: the plating in the step (2) is to be 0.1Adm at 40 ℃, current density
-2, the auxiliary stirring condition of 40KHz ultrasonic wave electroplated 10 minutes down.
The preparation-obtained tin nickel alloy negative material of lithium ion battery of present embodiment is compared with embodiment 2 preparation-obtained tin nickel alloy negative material of lithium ion battery, discharge capacity slightly improves but is more or less the same first, and follow-up cycle performance has clear improvement with respect to embodiment 3 gained electrodes.The discharge capacity attenuation curve of this tin nickel alloy negative material of lithium ion battery during as work electrode as shown in Figure 2, the about 570mAhg of initial discharge capacity as can be seen from Figure 2
-1, be more or less the same with the initial capacity of embodiment 2 electrodes, 30 times circulation back discharge capacity remains on 417mAhg
-1, cyclical stability obviously improves than embodiment 2.
Embodiment 6
Present embodiment except that following characteristics with embodiment 2: the K that is added
4P
2O
73H
2O is 0.5mol, NiCl6H
2O is 0.1mol, SnCl2H
2O is 0.15mol.
Embodiment 7
Present embodiment except that following characteristics with embodiment 2: the K that is added
4P
2O
73H
2O is that 1.4mol, glycine are 0.2mol, NiCl6H
2O is 0.34mol, SnCl2H
2O is 0.36mol.
The comparative example
Present embodiment except that following characteristics with embodiment 2: the NiCl6H that is added
2O is 0.45mol, does not add SnCl2H
2O, with the nickel sheet as anode.
Stanniferous not in the preparation-obtained lithium ion battery pure nickel negative material, its XRD figure spectrum as shown in Figure 1.The discharge capacity attenuation curve of this lithium ion battery pure nickel negative material during as work electrode as shown in Figure 2, the about 105mAhg of initial discharge capacity as can be seen from Figure 2
-1, be more or less the same with the initial capacity of embodiment 2 electrodes, 30 times circulation back discharge capacity remains on 30mAhg
-1, cyclical stability obviously improves than embodiment 2.
Tin content in the table 1 embodiment 1-4 lithium ion cell prepared tin nickel alloy negative material and with electroplate liquid in the relation of Sn/Ni mol ratio
| The embodiment numbering | Sn/Ni mol ratio in the electroplate liquid | Sn content in alloys (%) |
| 1 2 3 4 | 0.284 0.528 1.011 4.05 | 45.2 62.7 78.5 86.1 |
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1, a kind of preparation method of tin nickel alloy negative material of lithium ion battery comprises the steps:
(1) the preparation electroplate liquid makes the addition of each component in every liter of electroplate liquid as follows: SnCl2H
2O 0.10～0.36mol, NiCl6H
2O 0.09～0.35mol, K
4P
2O
73H
2O 0.5～1.5mol, glycine 0.1～0.2mol; Add NH then
4It is standby that OH regulates pH to 7.5～8.5;
(2) electroplate liquid for preparing in the step (1) being added in the electroplating bath, tin sheet and nickel sheet are linked together as anode, is negative electrode with the copper foil, is 0.05～0.15Adm at 30～45 ℃, current density
-2Condition under electroplated 5～10 minutes;
(3) cut a sheet after the copper foil clean dry after will electroplating and promptly make described tin nickel alloy negative material of lithium ion battery.
2, the preparation method of tin nickel alloy negative material of lithium ion battery according to claim 1 is characterized in that: Sn in the electroplate liquid of being prepared in the described step (1)
2+And Ni
2+Mol ratio be 0.25～4: 1.
3, the preparation method of tin nickel alloy negative material of lithium ion battery according to claim 1 is characterized in that: Sn in the electroplate liquid of being prepared in the described step (1)
2+And Ni
2+Total concentration be K
4P
2O
73H
21/2 of O concentration.
4, the preparation method of tin nickel alloy negative material of lithium ion battery according to claim 1 is characterized in that: copper foil adopts single face to electroplate in the described step (2).
5, the preparation method of tin nickel alloy negative material of lithium ion battery according to claim 1 is characterized in that: be to be 0.05～0.15Adm at 30～45 ℃, current density in the described step (2)
-2, the auxiliary stirring condition of ultrasonic wave electroplated 5～10 minutes down.
6, the preparation method of tin nickel alloy negative material of lithium ion battery according to claim 1 is characterized in that: described drying is vacuumize.
7, any lithium ion cell prepared tin nickel alloy negative material of claim 1～6 is characterized in that: contain Ni in the described tin nickel alloy negative material of lithium ion battery
3Sn
4Or the metastable phasing of NiSn.
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|---|---|---|---|
| CNA2008100259241A CN101237038A (en) | 2008-01-21 | 2008-01-21 | A tin nickel alloy negative material of lithium ion battery and its making method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570870B (en) * | 2009-05-05 | 2010-12-29 | 天津大学 | Corrosion resistant nickel-tin alloy plating solution and electroplating technology thereof |
| 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 |
| CN103066256A (en) * | 2013-01-04 | 2013-04-24 | 芜湖华欣诺电化学科技有限公司 | Preparation method for nanometer copper-tin nickel alloy cathode material, nanometer copper-tin nickel alloy cathode material and lithium ion battery |
| CN103114315A (en) * | 2013-03-11 | 2013-05-22 | 福建清景铜箔有限公司 | Chromate-free passivation method of copper foil |
| CN104393237A (en) * | 2014-09-30 | 2015-03-04 | 河南师范大学 | Stannum-base alloy negative plate for lithium ion battery and preparation method thereof |
| CN107316975A (en) * | 2017-07-26 | 2017-11-03 | 清华大学深圳研究生院 | A kind of sodium-ion battery negative plate |
| CN107611352A (en) * | 2017-09-19 | 2018-01-19 | 浙江众泰汽车制造有限公司 | A kind of spherical lithium ion battery negative material of nickel phosphorus oxygen micron and preparation method thereof and its negative electrode of lithium ion battery being prepared |
| CN107681136A (en) * | 2017-09-19 | 2018-02-09 | 浙江众泰汽车制造有限公司 | 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 |
| CN109478635A (en) * | 2016-10-05 | 2019-03-15 | 株式会社Lg化学 | Lithium metal secondary battery cathode and lithium metal secondary cell comprising it |
| CN111933919A (en) * | 2020-07-29 | 2020-11-13 | 拓米(成都)应用技术研究院有限公司 | Nano silicon powder, silicon-based negative electrode, lithium ion battery containing silicon-based negative electrode and manufacturing method of lithium ion battery |
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2008
- 2008-01-21 CN CNA2008100259241A patent/CN101237038A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570870B (en) * | 2009-05-05 | 2010-12-29 | 天津大学 | Corrosion resistant nickel-tin alloy plating solution and electroplating technology thereof |
| 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 |
| CN103066256A (en) * | 2013-01-04 | 2013-04-24 | 芜湖华欣诺电化学科技有限公司 | Preparation method for nanometer copper-tin nickel alloy cathode material, nanometer copper-tin nickel alloy cathode material and lithium ion battery |
| CN103066256B (en) * | 2013-01-04 | 2015-08-26 | 芜湖华欣诺电化学科技有限公司 | A kind of preparation method of Nanometer Copper-tin nickel alloy negative material, Nanometer Copper-tin nickel alloy negative material, lithium ion battery |
| CN103114315A (en) * | 2013-03-11 | 2013-05-22 | 福建清景铜箔有限公司 | Chromate-free passivation method of copper foil |
| CN103114315B (en) * | 2013-03-11 | 2015-03-25 | 福建清景铜箔有限公司 | Chromate-free passivation method of copper foil |
| CN104393237A (en) * | 2014-09-30 | 2015-03-04 | 河南师范大学 | Stannum-base alloy negative plate for lithium ion battery and preparation method thereof |
| CN109478635B (en) * | 2016-10-05 | 2022-04-08 | 株式会社Lg化学 | Negative electrode for lithium metal secondary battery and lithium metal secondary battery comprising same |
| US11522198B2 (en) | 2016-10-05 | 2022-12-06 | Lg Energy Solution, Ltd. | Negative electrode for lithium-metal secondary battery and lithium-metal secondary battery including the same |
| CN109478635A (en) * | 2016-10-05 | 2019-03-15 | 株式会社Lg化学 | Lithium metal secondary battery cathode and lithium metal secondary cell comprising it |
| CN107316975A (en) * | 2017-07-26 | 2017-11-03 | 清华大学深圳研究生院 | A kind of sodium-ion battery negative plate |
| CN107611352A (en) * | 2017-09-19 | 2018-01-19 | 浙江众泰汽车制造有限公司 | A kind of spherical lithium ion battery negative material of nickel phosphorus oxygen micron and preparation method thereof and its negative electrode of lithium ion battery being prepared |
| CN107681136B (en) * | 2017-09-19 | 2020-06-12 | 浙江众泰汽车制造有限公司 | Nickel-phosphorus-oxygen composite lithium ion battery cathode material, preparation method thereof and lithium ion battery cathode prepared from nickel-phosphorus-oxygen composite lithium ion battery cathode material |
| CN107611352B (en) * | 2017-09-19 | 2020-06-12 | 浙江众泰汽车制造有限公司 | Nickel-phosphorus-oxygen micron spherical lithium ion battery negative electrode material, preparation method thereof and lithium ion battery negative electrode prepared from nickel-phosphorus-oxygen micron spherical lithium ion battery negative electrode material |
| CN107681136A (en) * | 2017-09-19 | 2018-02-09 | 浙江众泰汽车制造有限公司 | 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 |
| CN111933919A (en) * | 2020-07-29 | 2020-11-13 | 拓米(成都)应用技术研究院有限公司 | Nano silicon powder, silicon-based negative electrode, lithium ion battery containing silicon-based negative electrode and manufacturing method of lithium ion battery |
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