CN103172120A - Preparation method of silicon-coated lithium ion battery anode material - Google Patents
Preparation method of silicon-coated lithium ion battery anode material Download PDFInfo
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- CN103172120A CN103172120A CN2013100431807A CN201310043180A CN103172120A CN 103172120 A CN103172120 A CN 103172120A CN 2013100431807 A CN2013100431807 A CN 2013100431807A CN 201310043180 A CN201310043180 A CN 201310043180A CN 103172120 A CN103172120 A CN 103172120A
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- lithium
- lithium manganate
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a silicon-coated lithium ion battery anode material. The preparation method comprises the following steps of: coating SiO2.nH2O on the surface of a lithium manganate matrix through chemical precipitation, wherein a low-sodium sodium silicate solution and a sulfuric acid solution are added to a high-speed stirring reaction kettle, which is used for mixing up lithium manganate LiMn2O4 sizing agent, for carrying out precipitation reaction; washing the discharged sizing agent after the silicon precipitate is sufficiently reacted; and drying at 100 DEG C to 150 DEG C after the solid-liquid separation to obtain the silicon dioxide-coated lithium manganate anode material. The preparation method disclosed by the invention is low in device requirements, simple in process and environment-friendly. And the anode material is long in cycle life and low in cost.
Description
Technical field
The present invention relates to a kind of preparation method of lithium manganate battery of coating modification method for preparing, especially coated Si of anode material of lithium battery.
Background technology
Lithium cell is as the environmental protection power supply of a new generation, and it has high energy density, the high advantages such as discharge platform, is widely used in 3C and the power tool electronic products such as mobile phone, camera, notebook computer.Along with the technical development of lithium cell, require it to have the characteristics such as high-energy, superpower, high cycle life and low cost.
The positive electrode material of lithium cell is the important component part of lithium cell, is the major effect factor of lithium cell performance, and present business-like positive electrode material mainly contains LiCoO
2, LiMn
2O
4, Li (NixCoyMnz) O
2, Li (NixCoyALz) O
2And LiFePO
4, the lithium manganate price is minimum, security and doubly forthright all better, but common lithium manganate exists John-Teller effect and Mn stripping, coats corrosion resistant SiO
2After, effectively block the reaction of manganese and HF, and can suppress the decomposition of electrolytic solution, the cycle life of material is obviously improved, be applied to power cycle field of batteries widely.
Lithium manganate cell positive electrode material is coated modification mainly to be comprised: coat Al
2O
3, ZnO, TiO
2, MgO, Sn O
2, CeO
2And Coated with Organic Matter, mostly be metal oxide and coat, coat post-processing temperature high, the material electric conductivity after it coats is all relatively poor, and material capacity decreases, and coating easily arrives inner and lithium manganate forms doping.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing anode material of lithium-ion battery of coated Si, the cycle life of positive electrode material is obviously improved.
Realize that technical scheme of the present invention is, have following steps and process,
Step 1: coat,
(1) get the raw materials ready, standby sodium silicate solution, i.e. Na
2OmSiO
2Solution, " m " expression mole number in formula, SiO
2Mass concentration is 3～8%; Standby sulphuric acid soln, h 2 so 4 concentration is 2～4%; Standby lithium manganate slurry, the lithium manganate solid content is 150～200g/L;
(2) reaction, i.e. silicon precipitin reaction, with sodium silicate solution together with sulphuric acid soln and stream add in the reactor that mixes up the lithium manganate slurry, heating, stirring, water glass and sulfuric acid 1:1 are reacted completely, and controlling the pH value is 9～10, and the time of silicon precipitin reaction is 1～4h;
(3) separate, after sufficient reacting is complete, carry out solid-liquid separation, get coated Si O
2.nH
2The lithium manganate of O, in formula, " n " is mole number;
Step 2: dehydration, with step 1 gained coated Si O
2.nH
2The lithium manganate of O drying and dehydrating in microwave drier, temperature are controlled at 100～150 ℃, namely get the lithium manganate of coated silica, i.e. LiMn
2O
4.x SiO
2, in formula, " x " is mole number.
Further, described sulphuric acid soln is that the dense bright sulfur acid of technical grade dilution forms; Described Na
2OmSiO
2Mole number m value preferred 3.0～3.4 in solution.
Further, described LiMn
2O
4XSiO
2Middle mole number x value preferred 2%～9%.
Further, preferred 120～200 r/min of described mixing speed, the temperature of described reaction preferably is controlled at 50～80 ℃.
Further, after drying and dehydrating is complete, the moisture＜preferred value 0.1% of the lithium manganate of described coated silica.
Coated Si O of the present invention
2For the surface coats, the subsequent disposal temperature is low, and positive electrode material good stability, the size distribution of producing are more even, sphericity improves, and granule interior is not exerted an influence, and can effectively extend the service life cycle of positive electrode material, and cost is lower, and over-all properties is good than the positive electrode material of other coatings.
Compare with additive method, the present invention has following advantage:
1. carry out the coating of silicon-dioxide, the subsequent disposal temperature is low, and can not be penetrated into granule interior affects structure generation, and the positive electrode material particle after coating is more even, and sphericity is better.
2. adopt the coating of silicon-dioxide, suppress the formation of passive film, can adsorb the moisture content of electrolytic solution, suppress electrolytic solution in the decomposition of electrode surface, effectively stop electrolytic solution to the corrosion of positive electrode material, the cycle life of positive electrode material is obviously improved.
3. coat as inorganic precipitation coats, more organic positive silicate class coats, and cost is low, and environmental pollution is little, and is easy to operate.Utilize microwave drying, treatment temp is low, less energy consumption, and cost is low.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
Fig. 2 is scanning electronic microscope (SEM) figure of the embodiment of the present invention 1.
Embodiment
The invention will be further described below in conjunction with embodiment." pure water " involved in the present invention mainly refers to resistance greater than the water of 18 megaohms, such as reaching requirement through remove the techniques such as metal ion and other negative and positive magazine ions except silt, carbon absorption, reverse osmosis membrane and electrophoresis.
Embodiment 1:
1. be ready to matrix lithium manganate 800kg, in the reactor of its input with high-speed stirring and chuck system, be mixed with slurry with pure water, its solid content is 160g/L.
2. contain 3% SiO of its molar weight according to the amount preparation of lithium manganate
2Sodium silicate solution, SiO
2Mass concentration be 5.3%, i.e. weighing Na
2O.3.1SiO
2Powder 10.6kg is formulated as the solution of 150 liters.
3. with pure water, sulfuric acid dilution being mixed with mass concentration is 3% solution.
Modulate the lithium manganate slurry, the pH value is controlled at 9.5, temperature is 70 ± 2 ℃, and mixing speed is 120r/min, by 2. solution, the 3. volume pump charging simultaneously of solution, 2. the input speed of solution water glass is 1.0L/min, system pH is controlled at 9.4～9.6, and the complete rear blowing of water glass reaction carries out solid-liquid separation, utilizes microwave to carry out drying slurry, drying temperature is 120 ℃, dry rear material moisture＜0.1%.Finished product is the lithium manganate that coats 3% silicon.
Embodiment 2:
1. be ready to matrix lithium manganate 800kg, in the reactor of its input with high-speed stirring and chuck system, be mixed with slurry with pure water, its solid content is 180g/L.
2. contain 4% SiO of its molar weight according to the amount preparation of lithium manganate
2Sodium silicate solution, SiO
2Mass concentration be 5.3%, i.e. weighing Na
2O.3.1SiO
2Powder 14.13kg is formulated as the solution of 200 liters.
3. with pure water, sulfuric acid dilution being mixed with mass concentration is 3% solution.
Modulate the lithium manganate slurry, the pH value is controlled at 9.6, temperature is 75 ± 2 ℃, and mixing speed is 120r/min, by 2. solution, the 3. volume pump charging simultaneously of solution, 2. the input speed of solution water glass is 1.5L/min, system pH is controlled at 9.5～9.7, and the complete rear blowing of water glass reaction carries out solid-liquid separation, utilizes microwave to carry out drying slurry, drying temperature is 120 ℃, dry rear material moisture＜0.1%.Finished product is the lithium manganate that coats 4% silicon.
Embodiment 3:
1. be ready to matrix lithium manganate 800kg, in the reactor of its input with high-speed stirring and chuck system, be mixed with slurry with pure water, its solid content is 180g/L.
2. contain 5% SiO of its molar weight according to the amount preparation of lithium manganate
2Sodium silicate solution, SiO
2Mass concentration be 6.6%, i.e. weighing Na
2O.3.1SiO
2Powder 17.7kg is formulated as the solution of 200 liters.
3. with pure water, sulfuric acid dilution being mixed with mass concentration is 3% solution.
Modulate the lithium manganate slurry, the pH value is controlled at 9.5, temperature is 70 ± 1 ℃, and mixing speed is 150r/min, by 2. solution, the 3. volume pump charging simultaneously of solution, 2. the input speed of solution water glass is 1.5L/min, system pH is controlled at 9.4～9.6, and the complete rear blowing of water glass reaction carries out solid-liquid separation, utilizes microwave to carry out drying slurry, drying temperature is 120 ℃, dry rear material moisture＜0.1%.Finished product is the lithium manganate that coats 5% silicon.
Embodiment 4:
1. be ready to matrix lithium manganate 800kg, in the reactor of its input with high-speed stirring and chuck system, be mixed with slurry with pure water, its solid content is 180g/L.
2. contain 6% SiO of its molar weight according to the amount preparation of lithium manganate
2Sodium silicate solution, SiO
2Mass concentration be
5.3%, i.e. weighing Na
2O3.1SiO
2Powder 21.2kg is formulated as the solution of 300 liters.
3. with pure water, sulfuric acid dilution being mixed with mass concentration is 3% solution.
Modulate the lithium manganate slurry, the pH value is controlled at 9.5, temperature is 70 ± 1 ℃, and mixing speed is 150r/min, by 2. solution, the 3. volume pump charging simultaneously of solution, 2. the input speed of solution water glass is 1.5L/min, system pH is controlled at 9.4～9.6, and the complete rear blowing of water glass reaction carries out solid-liquid separation, utilizes microwave to carry out drying slurry, drying temperature is 115 ℃, material moisture＜0.1%.Finished product is the lithium manganate that coats 6% silicon.
Embodiment 5:
1. be ready to matrix lithium manganate 800kg, in the reactor of its input with high-speed stirring and chuck system, be mixed with slurry with pure water, its solid content is 180g/L.
2. contain 8% SiO of its molar weight according to the amount preparation of lithium manganate
2Sodium silicate solution, SiO
2Mass concentration be 7.1%, i.e. weighing Na
2O3.1SiO
2Powder 28.3kg is formulated as the solution of 300 liters.
2. with pure water, sulfuric acid dilution being mixed with mass concentration is 3% solution.
Modulate the lithium manganate slurry, the pH value is controlled at 9.7, temperature is 80 ± 1 ℃, and mixing speed is 150r/min, by 2. solution, the 3. volume pump charging simultaneously of solution, 2. the input speed of solution water glass is 1.5L/min, system pH is controlled at 9.6～9.8, and the complete rear blowing of water glass reaction carries out solid-liquid separation, utilizes microwave to carry out drying slurry, drying temperature is 120 ℃, material moisture＜0.1%.Finished product is the lithium manganate that coats 8% silicon.
Claims (5)
1. the method for preparing anode material of lithium-ion battery of a coated Si, is characterized in that, has following steps and process,
Step 1: coat,
(1) get the raw materials ready, standby sodium silicate solution, i.e. Na
2OmSiO
2Solution, " m " expression mole number in formula, SiO
2Mass concentration is 3～8%; Standby sulphuric acid soln, h 2 so 4 concentration is 2～4%; Standby lithium manganate slurry, the lithium manganate solid content is 150～200g/L;
(2) reaction, i.e. silicon precipitin reaction, with sodium silicate solution together with sulphuric acid soln and stream add in the reactor that mixes up the lithium manganate slurry, heating, stirring, water glass and sulfuric acid 1:1 are reacted completely, and controlling the pH value is 9～10, and the time of silicon precipitin reaction is 1～4h;
(3) separate, after sufficient reacting is complete, carry out solid-liquid separation, get coated Si O
2.nH
2The lithium manganate of O, in formula, " n " is mole number;
Step 2: dehydration, with step 1 gained coated Si O
2.nH
2The lithium manganate of O drying and dehydrating in microwave drier, temperature are controlled at 100～150 ℃, namely get the lithium manganate of coated silica, i.e. LiMn
2O
4.x SiO
2, in formula, " x " is mole number.
2. the method for preparing anode material of lithium-ion battery of a kind of coated Si according to claim 1, is characterized in that, described sulphuric acid soln is that the dense bright sulfur acid of technical grade dilution forms; Described Na
2OmSiO
2In solution, mole number m value is 3.0～3.4.
3. the method for preparing anode material of lithium-ion battery of a kind of coated Si according to claim 1, is characterized in that, described LiMn
2O
4XSiO
2Middle mole number x value is 2%～9%.
4. the method for preparing anode material of lithium-ion battery of a kind of coated Si according to claim 1, is characterized in that, described mixing speed is 120～200 r/min, and the temperature of described reaction is controlled at 50～80 ℃.
5. the method for preparing anode material of lithium-ion battery of a kind of coated Si according to claim 1, is characterized in that, after described drying and dehydrating is complete, and the mangaic acid anode material for lithium-ion batteries moisture of described coated silica＜0.1%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105226250A (en) * | 2015-09-15 | 2016-01-06 | 施雨华 | Coated with silica combination electrode material and preparation method thereof |
| CN106076244A (en) * | 2016-06-12 | 2016-11-09 | 上海空间电源研究所 | A kind of preparation method of the long-life lithium ion sieve adsorbant of nano-oxide cladding |
| CN109095491A (en) * | 2018-08-29 | 2018-12-28 | 交城县金兰化工有限公司 | A kind of microwave dehydration method of the inorganic salts containing the crystallization water |
| CN109193041A (en) * | 2018-09-28 | 2019-01-11 | 山东天瀚新能源科技有限公司 | A kind of lithium ion battery that high temperature cyclic performance is excellent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1445311A (en) * | 2002-03-20 | 2003-10-01 | 新加坡纳米材料科技有限公司 | calcium carbonate/silicon dioxide-water(1/n) nano-compound particle and hollow silicon dioxide-water(1/n) nano-material and its preparation method |
| CN1569746A (en) * | 2004-04-29 | 2005-01-26 | 上海交通大学 | Method for preparing inorganic crystal whisker with SiO2-coated surface |
| CN102412395A (en) * | 2010-12-24 | 2012-04-11 | 无锡力泰能源科技股份有限公司 | Modified spinel lithium manganate for secondary lithium ion battery and preparation method thereof |
-
2013
- 2013-02-04 CN CN2013100431807A patent/CN103172120A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1445311A (en) * | 2002-03-20 | 2003-10-01 | 新加坡纳米材料科技有限公司 | calcium carbonate/silicon dioxide-water(1/n) nano-compound particle and hollow silicon dioxide-water(1/n) nano-material and its preparation method |
| CN1569746A (en) * | 2004-04-29 | 2005-01-26 | 上海交通大学 | Method for preparing inorganic crystal whisker with SiO2-coated surface |
| CN102412395A (en) * | 2010-12-24 | 2012-04-11 | 无锡力泰能源科技股份有限公司 | Modified spinel lithium manganate for secondary lithium ion battery and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105226250A (en) * | 2015-09-15 | 2016-01-06 | 施雨华 | Coated with silica combination electrode material and preparation method thereof |
| CN106076244A (en) * | 2016-06-12 | 2016-11-09 | 上海空间电源研究所 | A kind of preparation method of the long-life lithium ion sieve adsorbant of nano-oxide cladding |
| CN109095491A (en) * | 2018-08-29 | 2018-12-28 | 交城县金兰化工有限公司 | A kind of microwave dehydration method of the inorganic salts containing the crystallization water |
| CN109193041A (en) * | 2018-09-28 | 2019-01-11 | 山东天瀚新能源科技有限公司 | A kind of lithium ion battery that high temperature cyclic performance is excellent |
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Application publication date: 20130626 |