CN116779792A - Lithium ion battery anode material, preparation method and application - Google Patents
Lithium ion battery anode material, preparation method and application Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 54
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 131
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 60
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 59
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 8
- 229910052914 metal silicate Inorganic materials 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract 2
- 150000004706 metal oxides Chemical class 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000002994 raw material Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 239000011863 silicon-based powder Substances 0.000 claims description 12
- 238000006479 redox reaction Methods 0.000 claims description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 22
- 229910052749 magnesium Inorganic materials 0.000 description 22
- 239000002131 composite material Substances 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000011812 mixed powder Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 10
- 239000002344 surface layer Substances 0.000 description 8
- 238000001771 vacuum deposition Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
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- 230000000694 effects Effects 0.000 description 5
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 229910001947 lithium oxide Inorganic materials 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
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- 238000004626 scanning electron microscopy Methods 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
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- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- IPGANOYOHAODGA-UHFFFAOYSA-N dilithium;dimagnesium;dioxido(oxo)silane Chemical compound [Li+].[Li+].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IPGANOYOHAODGA-UHFFFAOYSA-N 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a metal doped silicon oxygen cathode material for a lithium ion battery, which is a particle material with a carbon layer coated on the surface, wherein the particles comprise nano silicon, metal silicate for introducing doped metal and silicon oxide; 100% of metal doped silicon oxygen cathode material, 1 to 15% of doped metal element, 1 to 10% of carbon element and 30 to 40% of oxygen element; the invention also discloses a preparation method of the anode material, which comprises the following process flow routes: the preparation method of the metal doped silicon oxide anode material mainly aims at solving the problems that in the existing preparation process of metal doped silicon oxide, the content of doping elements is difficult to control, the doping uniformity is poor and the utilization rate of metal elements is low.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a metal doped silicon oxygen cathode material for a lithium ion battery, a preparation method and application thereof.
Background
Silicon anodes (4200 mAh/g) are highly expected by academic and industry because of their specific capacity ten times that of graphite (372 mAh/g), however, the large volume change during charge and discharge is a major factor limiting their cycle life. Compared with pure silicon, the silicon oxide has higher specific capacity (2400 mAh/g) and excellent cycle performance, and is more hopeful to become a lithium ion battery cathode material for the next generation.
At present, the microstructure of the silicon oxide is not uniformly and clearly explained, a model with higher acceptance is that amorphous nano silicon is dispersed in a silicon dioxide substrate, and the existence of a silicon dioxide phase relieves the volume expansion of silicon particles in the lithium intercalation process, but also reacts with lithium to generate Li in the first lithium intercalation process 2 O and Li 4 SiO 4 Resulting in irreversible capacity loss, resulting in a lower initial coulombic efficiency of the silica. To address this problem, metal doping methods are generally employed to alleviate this problem.
Patent CN102214823B discloses a method for prelithiation of silicon oxide, which comprises mixing silicon oxide powder and LiH powder, performing heat treatment, and doping a small amount of metallic lithium into silicon oxide by using LiH with higher reducibility as a lithium source to compensate for irreversible lithium loss in the first charge and discharge process. The method can realize the improvement of the first coulomb efficiency, but the solid phase reaction has poor uniformity and low raw material utilization rate, meanwhile, the cost and the safety of LiH are to be questioned, and the industrialized amplification still has a larger problem.
Disclosure of Invention
The invention aims to provide a metal doped silicon oxygen anode material for a lithium ion battery, which has the advantages of accurate mixing proportion of silicon element, oxygen element and doped metal element and controllable material performance.
In order to solve the technical problem, the technical scheme of the invention is as follows: the metal doped silicon oxygen cathode material for lithium ion battery is a granular material with carbon layer coated on the surface, and the granules comprise nano silicon, metal silicate and silicon oxide;
100% of the total mass of the metal doped silicon oxygen anode material, 1 to 15% of doped metal element, 1 to 10% of carbon element and 30 to 40% of oxygen element.
The metal element is preferably one or two of Li, na, K, mg, al, ca, zn, cu, sn, ni. The invention utilizes redox reaction to effectively control the type of metal to be doped and the proportion of silicate.
Preferably, the nano-silicon crystal grain size is 10nm or less. In the invention, the silicon grain size is larger than 10nm, the specific capacity attenuation rate of the cathode material is obviously improved, and the cycle performance is poor; the silicon grain size was less than 1nm, and diffraction peaks of crystalline Si could not be detected in the XRD pattern. Preferably the silicon oxide is SiO z Wherein 0 < z < 2, preferably 0.5 < z < 1.5. The lower the oxygen content in the invention, the higher the specific capacity and first effect of the material, but the poorer the cycle performance; the higher the oxygen content, the better the cycle performance of the material but the lower the specific capacity and first effect.
The second purpose of the invention is to provide a preparation method of the metal doped silicon oxygen cathode material for the lithium ion battery, wherein the preparation process is controllable by uniformly mixing gas phase doped metal elements and gas phase silicon oxide with controllable oxidation-reduction reaction proportion.
In order to solve the technical problem, the technical scheme of the invention is as follows: the preparation method of the metal doped silicon oxygen cathode material for the lithium ion battery comprises the following steps:
step one, carrying out heat treatment on evenly mixed silicon powder and silicate powder containing metal to be doped under a vacuum condition to generate oxidation-reduction reaction, wherein the silicon powder reduces metal elements to be doped in the silicate in the oxidation-reduction reaction, and the reaction formula is as follows:
si (solid) +mM a O b ·nSiO 2 (solid state) →sio (gaseous) +m (gaseous);
step two, cooling and depositing the mixed gas of SiO and metal to be doped obtained in the step one, and collecting to obtain a solid mixed precursor containing metal elements to be doped and SiO;
step three, placing the precursor in an atmosphere furnace for secondary heat treatment to perform oxidation-reduction reaction to obtain a metal doped silica material;
the reaction formula is as follows:
m (solid) +SiO (solid) →M x SiO y (solid) +Si (solid).
The metal doped silica material obtained in step three of carbon-coated pulverization is preferred.
Preferably, the first step comprises silicate powder of more than two metals to be doped.
Preferably, the SiO powder or the raw material for preparing the SiO powder is additionally added in the raw material mixing stage. According to the invention, siO is supplemented by utilizing phase change in the oxidation-reduction reaction process in the step one and is mixed uniformly and in a controllable proportion in synchronization with the phase change of the metal to be doped, so that the performance of the obtained lithium ion battery anode material is adjusted.
Preferably, the molar ratio of the additionally supplemented SiO powder in the first step to Si in the first step is 0.3 to 0.8. The SiO supplemented in the invention plays a role in regulating and controlling the doping concentration of the metal element in the anode material, the lower the supplementing quantity is, the higher the doping concentration of the metal is, the higher the first effect of the material is, but the lower the capacity is; the larger the supplementing amount is, the lower the metal doping concentration is, the higher the capacity of the material is, but the first effect is not good.
The preferable technological conditions of the heat treatment in the first step are as follows:
the reaction temperature is 1200 ℃ to 1600 ℃;
the vacuum pressure in the chamber ranges from 1 Pa to 100Pa.
Preferably, the cool deposition temperature of step two is 400 ℃ to 800 ℃.
The preferable process conditions of the heat treatment in the third step are as follows:
the atmosphere is vacuum or nitrogen or argon inert gas atmosphere;
the heat treatment temperature is 600 ℃ to 1000 ℃;
the heat treatment time is 1h to 10h.
The third object of the invention is to provide a lithium ion battery, which has high coulomb efficiency for the first time and improved cycle performance.
In order to solve the technical problem, the technical scheme of the invention is as follows: the invention provides a metal doped silicon oxygen anode material for a lithium ion battery.
By adopting the technical scheme, the invention has the beneficial effects that:
the invention provides a preparation method of a metal doped silicon oxygen anode material for a lithium ion battery, which comprises the following steps: the preparation method of the metal doped silicon oxide anode material mainly aims at solving the problems that in the existing preparation process of metal doped silicon oxide, the content of doping elements is difficult to control, the doping uniformity is poor and the utilization rate of metal elements is low. The method adopts the mixture of silicate containing metal elements to be doped and simple substance silicon as raw materials, and the mixture is subjected to oxidation-reduction reaction under vacuum to synchronously generate metal simple substance vapor and silicon oxide vapor, so that the uniform mixing of the doped metal elements and the silicon oxide is realized, and the proportion is controllable. The metal doped silicon oxide anode material obtained by deposition has excellent electrochemical performance;
according to the method, conventional single-temperature-zone heating equipment is used, independent temperature control of raw materials for generating the silicon oxide and raw materials for generating metal element vapor to be doped by using multi-temperature-zone heating equipment is not needed, and the equipment requirements are reduced;
the metal doped silicon oxygen cathode material consists of metal silicate, silicon oxide, nano silicon and carbon.
The metal doped silicon oxygen cathode material is prepared by heating a mixture of simple substance silicon and silicate to generate oxidation-reduction reaction, synchronously generating silicon monoxide gas and metal simple substance gas, uniformly mixing, and then cooling and depositing. The material preparation method provided by the invention has the advantages that the utilization rate of raw materials is high, the doping amount is controllable, and the solid raw materials are completely gasified through high-temperature reaction to realize uniform mixing, so that the silicon, oxygen and metal elements in the obtained product are uniformly distributed.
The metal elements are uniformly distributed in the cathode material in the form of metal silicate, so that irreversible lithium loss in the first lithium intercalation process is reduced, volume change in the charge and discharge process is buffered, electrochemical agglomeration of nano silicon is inhibited, and the first coulomb efficiency and the cycle performance of the cathode material are improved.
Drawings
FIG. 1 is a result of XRD analysis of the magnesium-doped silicon oxygen anode material obtained in example 1;
FIG. 2 is a graph showing the results of SEM and EDS analysis of the magnesium-doped silicon oxygen anode material obtained in example 1;
fig. 3 is a charge-discharge curve when the magnesium-doped silicon oxide negative electrode material obtained in this example 1 was used as a negative electrode active component of a lithium ion battery;
fig. 4 is a graph showing the power cycle performance of the magnesium-doped silicon oxide negative electrode material obtained in example 1 as a negative electrode active ingredient of a lithium ion battery.
Detailed Description
In order to further explain the technical scheme of the invention, the invention is explained in detail by specific examples.
Example 1
The embodiment discloses a preparation method of a lithium ion battery anode material, which comprises the following steps:
step one, weighing 2 parts of micron-sized silicon powder (Si) and 1 part of magnesium silicate powder (MgSiO) according to a molar ratio of 2:1 3 ) Mixing for 48 hours in a V-shaped mixer to obtain uniformly mixed powder raw materials;
adding the mixed powder raw materials into a high temperature region of a vacuum deposition furnace, and additionally adding SiO powder, wherein the molar ratio of SiO to Si is 0.75; vacuumizing to below 10Pa, and heating to 1400 ℃ at 10 ℃/min to react the raw materials;
condensing and depositing the generated magnesium and silicon oxide mixed vapor in a collecting area to obtain a massive magnesium doped silicon oxide composite material, wherein the pressure in a furnace chamber of a reaction process monitored by a pressure gauge is 20Pa, and the deposition temperature of the collecting area is 600 ℃;
transferring the massive magnesium doped silicon oxide composite material obtained in the collecting area into an atmosphere furnace for secondary heat treatment, vacuumizing to below 10Pa, and heating to 900 ℃ at 10 ℃/min for 2h;
step four, crushing the bulk magnesium doped silicon oxide composite material subjected to the secondary heat treatment by adopting air flow to obtain a particle size (D50) of 5 mu m;
adding 5 mu m magnesium doped silica powder into a coating furnace, and carrying out gas-phase carbon coating at 900 ℃ by taking methane as a carbon source to obtain the magnesium doped silicon oxygen anode material with the uniform carbon coating on the surface layer.
Elemental content measurement was performed on the magnesium-doped silicon-oxygen anode material obtained in this example 1, wherein the C content was 5.0% of the total mass of the magnesium-doped silicon-oxygen anode material, the O content was 31.7% and the Mg content was 6.9%.
Example 2
The embodiment discloses a preparation method of a lithium ion battery anode material, which comprises the following steps:
step one, weighing 2 parts of silicon powder (Si) and 1 part of lithium silicate powder (Li 2 SiO 3 ) Mixing for 48 hours in a V-shaped mixer to obtain uniformly mixed powder raw materials;
adding the mixed powder raw materials into a high temperature region of a vacuum deposition furnace, and additionally adding SiO powder, wherein the molar ratio of the SiO powder to Si is 0.75; vacuumizing to below 10Pa, and heating to 1300 ℃ at 10 ℃/min to react the raw materials to generate lithium and silicon oxide mixed vapor;
condensing and depositing the generated mixed vapor of lithium and silicon oxide in a collecting area to obtain a blocky lithium doped silicon oxide composite material, wherein the pressure in a furnace chamber of a reaction process monitored by a pressure gauge is 20Pa, the collecting area is cooled in an air cooling mode, and the deposition temperature is 400 ℃;
transferring the blocky lithium doped silicon oxide composite material obtained in the collecting area into an atmosphere furnace for secondary heat treatment, vacuumizing to below 10Pa, and heating to 600 ℃ at 10 ℃/min for 10h;
step four, crushing the blocky lithium doped silicon oxide composite material subjected to the secondary heat treatment by adopting air flow to obtain a particle size (D50) of 5 mu m;
adding lithium doped silicon oxide powder with the particle size of 5 mu m into a coating furnace, and carrying out gas-phase carbon coating at the temperature of 900 ℃ by taking methane as a carbon source to obtain the lithium doped silicon oxide anode material with the uniform carbon coating on the surface layer.
The element content of the lithium-doped silicon-oxygen anode material obtained in the embodiment is measured, wherein the content of C accounts for 3.1% of the total mass of the lithium-doped silicon-oxygen anode material, the content of O accounts for 32.9%, and the content of Li accounts for 5.1%.
Example 3
The embodiment discloses a preparation method of a lithium ion battery anode material, which comprises the following steps:
step one, weighing micron-sized silicon powder (Si) and magnesium silicate powder (MgSiO) according to a molar ratio of 2:1 3 ) Mixing for 48 hours in a V-shaped mixer to obtain uniformly mixed powder raw materials;
adding the mixed powder raw materials into a high temperature region of a vacuum deposition furnace,no additional SiO powder is addedVacuumizing to below 10Pa, and heating to 1400 ℃ at 10 ℃/min to react the raw materials to generate magnesium and silicon oxide mixed vapor.
Condensing and depositing the obtained mixed vapor in a collecting area to obtain a massive magnesium doped silicon oxide composite material, wherein the pressure in a furnace chamber of a reaction process monitored by a pressure gauge is 10Pa, and the depositing temperature of the collecting area is 600 ℃;
transferring the massive magnesium doped silicon oxide composite material obtained in the collecting area into an atmosphere furnace for secondary heat treatment, adopting nitrogen as a protective atmosphere, and heating to 900 ℃ at 10 ℃/min for 2h;
step four, crushing the bulk magnesium doped silicon oxide composite material subjected to the secondary heat treatment by adopting air flow to obtain a particle size (D50) of 5 mu m;
adding 5 mu m magnesium doped silica powder into a coating furnace, and carrying out gas-phase carbon coating at 900 ℃ by taking methane as a carbon source to obtain the magnesium doped silicon oxygen anode material with the uniform carbon coating on the surface layer.
The elemental content of the magnesium-doped silicon-oxygen anode material obtained in this example was measured, wherein the content of C was 5.2% of the total mass of the magnesium-doped silicon-oxygen anode material, the content of O was 32.8%, and the content of Mg was 12.5%.
Example 4
The embodiment discloses a preparation method of a lithium ion battery anode material, which comprises the following steps:
step one, weighing 6 parts of silicon powder (Si) and 1 part of magnesium lithium silicate powder (Li 2 O·2MgO·3SiO 2 ) Mixing for 48 hours in a V-shaped mixer to obtain uniformly mixed powder raw materials;
adding the mixed powder raw materials into a high temperature region of a vacuum deposition furnace, and additionally adding SiO powder, wherein the molar ratio of SiO to Si is 1:3; vacuumizing to below 10Pa, and heating to 1500 ℃ at 10 ℃/min to react the raw materials to generate mixed vapor of lithium, magnesium and silicon oxide;
condensing and depositing the mixed vapor in a collecting area to obtain a blocky lithium-magnesium doped silicon oxide composite material, wherein the pressure in a furnace chamber of a reaction process monitored by a pressure gauge is 20Pa, the collecting area is cooled in an air cooling mode, and the deposition temperature is 500 ℃;
transferring the blocky lithium-magnesium doped silicon oxide composite material obtained in the collecting area into an atmosphere furnace for secondary heat treatment, adopting argon as a protective atmosphere, and heating to 800 ℃ at 10 ℃/min for 5h;
step four, crushing the blocky lithium-magnesium doped silicon oxide composite material subjected to the secondary heat treatment by adopting air flow to obtain a particle size (D50) of 5 mu m;
adding lithium-magnesium doped silica powder with the particle size of 5 mu m into a coating furnace, and carrying out gas-phase carbon coating at 900 ℃ by taking methane as a carbon source to obtain the lithium-magnesium doped silica anode material with the uniform carbon coating on the surface layer.
The element content of the lithium-doped silicon-oxygen anode material obtained in the embodiment was measured, wherein the content of C was 4.7% of the total mass of the lithium-doped silicon-oxygen anode material, the content of O was 33.4%, the content of Li was 2.1%, and the content of Mg was 7.3%.
Example 5
The embodiment discloses a preparation method of a lithium ion battery anode material, which comprises the following steps:
step one, weighing 6 parts of silicon powder (Si) and 1 part of magnesium aluminum silicate powder (Al 2 O 3 ·3MgO·3SiO 2 ) Mixing for 48 hours in a V-shaped mixer to obtain uniformly mixed powder raw materials;
adding the mixed powder raw materials into a high temperature region of a vacuum deposition furnace, and additionally adding SiO powder, wherein the molar ratio of SiO to Si is 5:6, preparing a base material; vacuumizing to below 10Pa, and heating to 1400 ℃ at 10 ℃/min to react the raw materials to generate mixed vapor of magnesium, aluminum and silicon oxide;
condensing and depositing the mixed vapor in a collecting area to obtain a massive magnesium-aluminum doped silicon oxide composite material, wherein the pressure in a furnace chamber of a reaction process monitored by a pressure gauge is 20Pa, the collecting area is cooled in a water cooling mode, and the deposition temperature is 500 ℃;
transferring the massive magnesium-aluminum doped silica composite material obtained in the collecting area into an atmosphere furnace for secondary heat treatment, adopting nitrogen as a protective atmosphere, and heating to 900 ℃ at 10 ℃/min for 2h;
step four, crushing the massive magnesium aluminum doped silicon oxide composite material subjected to the secondary heat treatment by adopting air flow to obtain a particle size (D50) of 5 mu m;
adding 5 mu m magnesia-alumina doped silica powder into a coating furnace, and carrying out gas-phase carbon coating at 900 ℃ by taking methane as a carbon source to obtain the magnesia-alumina doped silica anode material with the uniform carbon coating surface layer.
The element content of the lithium-doped silicon-oxygen anode material obtained in the embodiment is measured, wherein the content of C is 5.0% of the total mass of the lithium-doped silicon-oxygen anode material, the content of O is 32.2%, the content of Al is 4.6%, and the content of Mg is 6.8%.
Example 6
The embodiment discloses a preparation method of a lithium ion battery anode material, which comprises the following steps:
step one, weighing 4 parts of silicon powder (Si) and 1 part of lithium silicate powder (Li) according to a molar ratio 2 SiO 3 ) And magnesium silicate powder (MgSiO 3), mixing for 48 hours in a V-shaped mixer to obtain uniformly mixed powder raw materials;
adding the mixed powder raw materials into a high temperature region of a vacuum deposition furnace, and additionally adding SiO powder, wherein the molar ratio of SiO to Si is 3:8; vacuumizing to below 10Pa, and heating to 1400 ℃ at 10 ℃/min to react the raw materials to generate mixed vapor of lithium, magnesium and silicon oxide;
condensing and depositing the mixed vapor in a collecting area to obtain a blocky lithium-magnesium doped silicon oxide composite material, wherein the pressure in a furnace chamber of a reaction process monitored by a pressure gauge is 20Pa, the collecting area is cooled in an air cooling mode, and the deposition temperature is 600 ℃;
transferring the blocky lithium-magnesium doped silicon oxide composite material obtained in the collecting area into an atmosphere furnace for secondary heat treatment, adopting argon as a protective atmosphere, and heating to 1000 ℃ at 10 ℃/min for heat preservation for 1h;
step four, crushing the blocky lithium-magnesium doped silicon oxide composite material subjected to the secondary heat treatment by adopting air flow to obtain a particle size (D50) of 5 mu m;
adding lithium-magnesium doped silica powder with the particle size of 5 mu m into a coating furnace, and carrying out gas-phase carbon coating at 900 ℃ by taking methane as a carbon source to obtain the lithium-magnesium doped silica anode material with the uniform carbon coating on the surface layer.
The element content of the lithium-doped silicon-oxygen anode material obtained in the embodiment is measured, wherein the content of C is 5.2% of the total mass of the lithium-doped silicon-oxygen anode material, the content of O is 33.9%, the content of Li is 3.1%, and the content of Mg is 5.5%.
Comparative example 1
The magnesium doped silicon oxide is prepared by adopting metal magnesium as a magnesium source, and the specific preparation method is as follows:
1. according to the mol ratio of 1:1:0.4 weighing micron-sized silicon powder (Si), silicon dioxide powder (SiO 2 ) And metal magnesium powder (Mg), mixing for 48 hours in a V-shaped mixer to obtain uniformly mixed powder raw materials;
2. adding the mixed powder raw materials into a high-temperature region of a vacuum deposition furnace, vacuumizing to below 10Pa, heating to 1400 ℃ at 10 ℃/min to react the raw materials, condensing and depositing the generated silica vapor and magnesium vapor in a collecting region to obtain a massive magnesium-doped silica material, wherein the internal pressure of a furnace chamber of a reaction process monitored by a pressure gauge is 10Pa, and the depositing temperature of the collecting region is 600 ℃;
3. crushing the magnesium doped silicon oxide material to a particle size (D50) of 5 mu m by adopting air flow;
4. adding 5 mu m magnesium doped silica powder into a coating furnace, and carrying out gas-phase carbon coating at 900 ℃ by taking methane as a carbon source to obtain the magnesium doped silicon oxygen anode material with the uniform carbon coating on the surface layer.
The elemental content of the magnesium-doped silicon-oxygen anode material obtained in this comparative example 1 was measured, wherein the content of C was 4.8% of the total mass of the lithium-doped silicon-oxygen anode material, the content of O was 34.5%, and the content of Mg was 1.2%.
Comparative example 2
Preparing metal-free doped silicon oxide, and adopting methane as a carbon source to carry out gas-phase carbon coating, wherein the preparation method comprises the following steps of:
(1) Weighing micron-sized silicon powder (Si) and silicon dioxide powder (SiO) according to a molar ratio of 1:1 2 ) Mixing for 48 hours in a V-shaped mixer to obtain uniformly mixed powder raw materials;
(2) Adding the mixed powder raw materials into a high-temperature region of a vacuum deposition furnace, vacuumizing to below 10Pa, heating to 1400 ℃ at 10 ℃/min to react the raw materials, condensing and depositing the generated silica vapor in a collecting region to obtain a massive silica material, wherein the internal pressure of a furnace chamber of a reaction process monitored by a pressure gauge is 10Pa, and the depositing temperature of the collecting region is 600 ℃;
(3) Crushing the massive silicon oxide material by adopting air flow to obtain a particle size (D50) of 5 mu m;
(4) Adding the 5 mu m silicon oxide powder into a coating furnace, and carrying out gas-phase carbon coating at 900 ℃ by taking methane as a carbon source to obtain the silicon oxide anode material with the uniform carbon coating on the surface layer.
The element content of the lithium-doped silicon-oxygen anode material obtained in the comparative example 2 was measured, wherein the C content was 5.2% of the total mass of the lithium-doped silicon-oxygen anode material, and the O content was 35.2%
The following characterization was performed for the negative electrode materials prepared in examples 1 to 6 and comparative examples 1 and 2:
1) Phase analysis
To analyze the phase structure of the product of the examples, X-ray diffraction (XRD) analysis was performed. Si grain size was analyzed using the scherrer equation(s) based on the Si (111) peak ascribed to the vicinity of 28.5 ° in the XRD pattern:
Crystal size (nm) = K·λ/(B·cosθ)；
where k=0.9, λ=0.154 nm, b=half width (FWHM, rad), θ=peak position (angle).
2) Morphology and particle size analysis
And analyzing the microscopic morphology of the material by adopting a Scanning Electron Microscope (SEM), analyzing the distribution condition of metal, silicon and oxygen elements in particles by adopting an energy spectrum (EDS) surface scanning, and measuring the particle size distribution of the material by adopting a Markov laser particle sizer.
3) O, C and determination of the content of metallic elements
And (3) measuring the content of metal elements in the sample by adopting an inductively coupled plasma emission spectrometry (ICP-OES), measuring the content of C elements in the sample by adopting a sulfur-carbon analyzer, and measuring the content of O elements in the sample by adopting a LECO oxygen content analyzer. The metal element utilization rate is calculated based on the following formula:
metal element utilization = (total mass of product x metal element content)/mass of metal element in raw material
4) Electrochemical performance test
Taking the magnesium doped silicon oxygen anode material as an anode active component, and mixing the anode active component with a conductive agent SP and a binder LA136D according to the mass ratio of 80:10:10, mixing the slurry. Coating the prepared slurry on copper foil, drying, rolling and slicing, adopting a metal lithium sheet as a counter electrode, assembling into a button cell, and then carrying out electrochemical performance test, wherein the electrolyte is 1M LiPF 6 The solution, solvent, was formulated with EC/EMC/dmc=1/1/1. The charge-discharge cycle test was performed at a rate of 0.1C (1C =1500 mAh/g), with a voltage interval of 1.5 to 0.005V.
As shown in FIGS. 1 to 4, FIG. 1 shows XRD analysis results of the magnesium-doped silicon oxide anode material obtained in example 1, in which the (111) peak attributed to Si crystal was present in the vicinity of the diffraction angle (2θ) 28.5℃and the MgSiO was present in the vicinity of the diffraction angle (2θ) 31.1 ° 3 Peak (610) of the crystal. In addition, amorphous silicon oxide (corresponding to between 17 and 25 DEG in XRD) is also present in the magnesium-doped silicon oxide negative electrode materialBroad peak of (c). Fig. 2 shows SEM and EDS analysis results of the magnesium-doped silicon oxide anode material obtained in this example 1, in which the doped Mg element and Si and O elements are uniformly distributed in the micrometer-sized material particles. Fig. 3 is a charge-discharge curve when the magnesium-doped silicon oxide negative electrode material obtained in example 1 is used as a negative electrode active component of a lithium ion battery, and the result shows that the material has good lithium intercalation and deintercalation performance. Fig. 4 is a graph showing the buckling cycle performance curve of the magnesium-doped silicon oxygen anode material obtained in the present example 1 as the anode active component of the lithium ion battery, and as a result, the reversible capacity of the material is hardly attenuated after 30 cycles, and excellent electrochemical performance is shown.
Electrochemical performance tests were further performed on the lithium ion batteries corresponding to examples 1 to 6 and comparative examples 1 and 2, and specific test data are shown in table 1.
Table 1 list of electrochemical performance data of the anode material metal doping cases and corresponding batteries in examples 1 to 6 and comparative examples 1 and 2
As is apparent from the above examples and comparative example 2, the metal-doped silicon negative electrode material has significantly improved initial coulombic efficiency as compared with the undoped silicon negative electrode material, and exhibits more excellent cycle performance. The larger the metal doping amount is, the higher the first effect of the material is, but the capacity is reduced, and meanwhile, excessive growth of Si grains is caused, so that the cycle performance is damaged. The lithium single component doping exhibits optimal capacity and cycling performance. Considering the high raw material cost of the metallic lithium, the addition of the second component metallic element to replace part of lithium can greatly reduce the manufacturing cost of the material and maintain better electrochemical performance.
In comparative example 1, silicon and silicon dioxide react to generate SiO vapor at an initial temperature of about 1300 ℃, the boiling point of magnesium metal is about 1100 ℃, and the gasification rate under vacuum is faster, so that the magnesium metal is gasified in advance, a small part of the magnesium metal can enter SiO gas, the utilization rate of a magnesium source is low, and the distribution of Mg in deposited materials is uneven. The dissipated Mg vapor can be deposited inside the hearth and on the surface of the heating element, so that damage and potential safety hazards are caused; the preparation method provided by the invention adopts the reaction of silicon and metal silicate, and the metal silicate is used as a metal source at the temperature of more than 1300 ℃, and simultaneously generates SiO vapor and metal vapor, so that the uniform mixing of two gaseous products is realized, the synchronous cooling deposition is realized, the utilization rate of metal elements is greatly improved, and the metal elements in the deposited products are uniformly distributed. As can be seen from the comparison, in the comparative example 1, the metal magnesium simple substance is adopted as the magnesium source for doping, most of metal elements do not enter into the silicon because the metal simple substance has low boiling point and is extremely easy to gasify, and the utilization rate is low.
Claims (13)
1. A metal doped silicon oxygen cathode material for a lithium ion battery is characterized in that: the surface of the material is coated with a carbon layer, and the particles comprise nano silicon, metal silicate for introducing doped metal and silicon oxide;
100% of the total mass of the metal doped silicon oxygen anode material, 1 to 15% of doped metal element, 1 to 10% of carbon element and 30 to 40% of oxygen element.
2. The anode material according to claim 1, characterized in that: the metal element is one or two of Li, na, K, mg, al, ca, zn, cu, sn, ni.
3. The anode material according to claim 1, characterized in that: the nano silicon grain size is below 10 nm.
4. The anode material according to claim 1, characterized in that: silicon oxide is SiO z Wherein 0 < z < 2.
5. A method for preparing the anode material according to claim 1, characterized in that:
the method comprises the following steps:
step one, carrying out heat treatment on evenly mixed silicon powder and silicate powder containing metal to be doped under a vacuum condition to generate oxidation-reduction reaction, wherein the silicon powder reduces metal elements to be doped in the silicate in the oxidation-reduction reaction, and the reaction formula is as follows:
si (solid) +mM a O b ·nSiO 2 (solid state) →sio (gaseous) +m (gaseous);
step two, cooling and depositing the mixed gas of SiO and metal to be doped obtained in the step one, and collecting to obtain a solid mixed precursor containing metal elements to be doped and SiO;
step three, placing the precursor in an atmosphere furnace for secondary heat treatment to perform oxidation-reduction reaction to obtain a metal doped silica material;
the reaction formula is as follows:
m (solid) +SiO (solid) →M x SiO y (solid) +Si (solid).
6. The method of manufacturing according to claim 5, wherein:
and (3) coating and crushing the metal doped silica material obtained in the step three by carbon.
7. The method of manufacturing according to claim 5, wherein: the first step comprises silicate powder of more than two metals to be doped.
8. The method of manufacturing according to claim 5, wherein: and in the first raw material mixing stage, siO powder or raw materials for preparing the SiO powder are additionally added.
9. The method of manufacturing according to claim 5, wherein: the molar ratio of the additionally supplemented SiO powder in the first step to Si in the first step is 0.3 to 0.8.
10. The method of manufacturing according to claim 5, wherein: the heat treatment process conditions in the first step are as follows:
the reaction temperature is 1200 ℃ to 1600 ℃;
the vacuum pressure in the chamber ranges from 1 Pa to 100Pa.
11. The method of manufacturing according to claim 5, wherein: the cooling deposition temperature of the second step is 400-800 ℃.
12. The method of manufacturing according to claim 5, wherein: the heat treatment process conditions in the third step are as follows:
the atmosphere is vacuum or nitrogen or argon inert gas atmosphere;
the heat treatment temperature is 600 ℃ to 1000 ℃;
the heat treatment time is 1h to 10h.
13. A lithium ion battery, characterized in that: a negative electrode material according to any one of claims 1 to 4.
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