CN102664247B - Method for preparing LiFePO4/SiC lithium battery positive plate by microwave heating - Google Patents
Method for preparing LiFePO4/SiC lithium battery positive plate by microwave heating Download PDFInfo
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- CN102664247B CN102664247B CN201210094656.5A CN201210094656A CN102664247B CN 102664247 B CN102664247 B CN 102664247B CN 201210094656 A CN201210094656 A CN 201210094656A CN 102664247 B CN102664247 B CN 102664247B
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- China
- Prior art keywords
- sic
- lifepo4
- lifepo
- positive plate
- lithium battery
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000010438 heat treatment Methods 0.000 title claims abstract description 9
- 229910052493 LiFePO4 Inorganic materials 0.000 title abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 239000006258 conductive agent Substances 0.000 claims abstract description 5
- 238000005520 cutting process Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 21
- 229910010710 LiFePO Inorganic materials 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052912 lithium silicate Inorganic materials 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000498 ball milling Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 15
- 229910010271 silicon carbide Inorganic materials 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a LiFePO4/SiC lithium battery positive plate by microwave heating. The method is characterized in that: the method comprises the following steps of 1, immersing LiFePO4 in a lithium silicate aqueous solution having mass concentration of 20 to 30% for 2 to 5 hours, fully stirring and evaporating water of the lithium silicate aqueous solution, 2, carrying out calcination of the immersed LiFePO4 at a temperature of 500 DEG C for 2 to 5 hours, 3, adding SiC having particle sizes of 100 to 150 microns into LiFePO4 powder obtained by calcination, wherein a use mount of SiC is 5 to 10wt% of that of LiFePO4, and carrying out uniform ball-milling mixing, 4, heating the mixture obtained by the step 3 in a microwave oven under the conditions of microwave power of 300 to 500W and heating time of 10 to 25 minutes, and 5, mixing the mixture obtained by the step 4, a binder, a conductive agent, an additive and a solvent into slurry, and carrying out coating, drying, rolling and cutting of the slurry to obtain the LiFePO4/SiC lithium battery positive plate. The method can effectively solve the problem of falling-off of LiFePO4 powder in coating and assembling and can obviously improve electrochemical performances of the LiFePO4/SiC lithium battery positive plate, and is simple in application and low in cost.
Description
Technical field
The present invention relates to a kind of manufacture method of ferric phosphate lithium cell, relate in particular to a kind of microwave heating and prepare LiFePO
4the method of/SiC positive plate of lithium battery.
Background technology
The advantages such as lithium ion battery has that operating voltage is high, energy density is large, have extended cycle life, self-discharge rate is little, environmental protection, become the trend of secondary cell development.Now be widely used in the power supply of the portable electricity consuming productses such as wireless telecommunications, digital camera, notebook computer, and had broad application prospects aspect the large capacity power source of special application field such as Aero-Space, defence and military, field work, submarine.
Due to LiCoO
2shortage of resources, expensive, particularly its poor stability, has limited its application in electrokinetic cell field.LiFePO4 is because of its abundant raw material, and fail safe is good, has been widely regarded as the first-selected positive electrode of lithium-ion-power cell of future generation.But lithium iron phosphate positive material also has a fatal shortcoming, that is exactly that conductivity is low, and this shortcoming has greatly affected LiFePO
4application.At present, in order to overcome this shortcoming, people have taked following technical measures: prepare ultra-fine grain, increase the specific area of material or the carbon that coated one deck can conduct electricity, use LiPF
6as electrolyte solution, to improve its conductivity.But, the LiFePO of fine particle
4in coating and assembling process, bring again the problem of the easy dry linting of pole piece; Use LiPF
6as electrolyte solution, its HF that decomposes out can with from LiFePO
4the Li deviating from
+reaction, has reduced LiFePO
4gram volume, and then affect its energy density.Therefore, the problem such as pole piece dry linting and low gram volume has had a strong impact on LiFePO
4the development of battery technology.
CN 200610157460.0 discloses a kind of manufacture method of positive plate of iron phosphate lithium battery, and the method is before LiFePO4 slurry is coated to collector, first aqueous slkali is sprayed on to collection liquid surface or collector is soaked in to 5-60 second in aqueous slkali.The method has certain effect to solving pole piece dry linting problem, but still owes desirable, and operating procedure complexity; And the ferric phosphate lithium cell of the positive plate of manufacturing by the method assembling, gram volume has no raising.
Summary of the invention
The present invention is directed to problems of the prior art, provide a kind of microwave heating to prepare LiFePO
4the method of/SiC positive plate of lithium battery, the gram volume of this positive plate has had and has significantly improved, and can effectively improve the dry linting phenomenon in coating and assembling process, and easy to operation, with low cost.
Technical scheme of the present invention is to comprise the following steps:
(1) by LiFePO
4the lithium metasilicate aqueous solution that is placed in mass concentration and is 20-30% soaks 2-5h, and fully stirs, and solution moisture content testing is evaporated;
(2) by the LiFePO after soaking
4roasting 2-5h at 500 DEG C;
(3) at the LiFePO through roasting gained
4in powder, the particle diameter that to add with respect to the content of LiFePO4 be 5-10wt% is the SiC of 100-150 μ m, carries out ball milling and mixes;
(4) mixture step (3) being obtained is heating in microwave oven, and microwave power is adjusted to 300-500W, and the control time is 10-25 minute;
(5) mixture obtaining again with the mixed preparing form slurry such as binding agent, conductive agent, additive, solvent, through being coated with, being dried, roll film, cutting, be made into LiFePO
4/ SiC positive plate of lithium battery.
In embodiment further, the particle diameter of described SiC is preferably 150 μ m; Described microwave power is preferably adjusted to 500W; Described lithium metasilicate concentration of aqueous solution is preferably 30%; The roasting time of described step (2) is preferably 5h; The content of described SiC is preferably 10wt%; The control time of described step (4) is preferably 10 minutes.
The present invention has the following advantages and good effect: join the lithium metasilicate aqueous solution in positive electrode, in coating process, can corrode collector aluminium foil, increase the roughness of aluminium foil, thereby make LiFePO
4be more prone to be attached on collector, thus the phenomenon of minimizing pole piece dry linting; The lithium metasilicate aqueous solution joining in positive electrode is alkaline matter, can be effectively with electrolyte in HF reaction, and then reduce HF with from LiFePO
4the Li deviating from
+reaction, thus the gram volume of LiFePO4 improved; The present invention adopts SiC to be coated LiFePO
4due to the increase along with silicon-carbide particle size, its electric conductivity also increases, preferred dimension of the present invention be the SiC of 100 μ m as raw material, improve greatly the chemical property of anode material of lithium battery; The present invention is easy to operation, with low cost.
Embodiment
Embodiment 1
(1) by common commercially available LiFePO
4be placed in mass concentration and be 20% alumina silicate and soak 3h, and fully stir, solution moisture content testing is evaporated; (2) by the LiFePO after soaking
4roasting 2h at 500 DEG C; (3) at the LiFePO through roasting gained
4in powder, add with respect to LiFePO
4content be 5wt% particle diameter is the SiC of 100 μ m, the mixture obtaining is being heated in microwave oven, microwave power is adjusted to 500W, control time is 25 minutes, again with mixed preparing form slurry such as binding agent, conductive agent, additive, solvents, through being coated with, being dried, roll film, cutting, be made into LiFePO
4/ SiC positive plate of lithium battery.
The based lithium-ion battery positive plate that adopts the present embodiment to produce, according to the common process of producing lithium ion battery, assemble with negative plate, barrier film, electrolyte, battery case, the lithium iron phosphate dynamic battery obtaining after discharging and recharging activation, the based lithium-ion battery positive plate assembling lithium iron phosphate dynamic battery that adopts the present embodiment to produce, after testing, the gram volume of positive plate dry linting amount and LiFePO4 is shown in this specification end subordinate list 1,2.
Embodiment 2
(1) by common commercially available LiFePO
4be placed in mass concentration and be 30% Li
2cO
3in solution, soak 3h, and fully stir, solution moisture content testing is evaporated; (2) by the LiFePO after soaking
4roasting 5h at 500 DEG C; (3) at the LiFePO through roasting gained
4in powder, add with respect to LiFePO
4the content of positive active material is that the particle diameter of 10wt% is the SiC of 150 μ m, the mixture obtaining is being heated in microwave oven, microwave power is adjusted to 500W, control time is 10 minutes, again with mixed preparing form slurry such as binding agent, conductive agent, additive, solvents, through being coated with, being dried, roll film, cutting, be made into LiFePO
4/ SiC positive plate of lithium battery.
The lithium iron phosphate dynamic battery that the based lithium-ion battery positive plate that adopts the present embodiment to produce is assembled into, after testing, the gram volume of positive plate dry linting amount and LiFePO4 is shown in this specification end subordinate list 1,2.
Table 1 embodiment 1-2 positive plate dry linting amount
| Embodiment | 1 | 2 | Contrast conventional method |
| Dry linting rate (%) | 1.0 | 0.8 | 6.3 |
The gram volume of table 2 embodiment 1-2 positive plate LiFePO4
| Embodiment | 1 | 2 | Contrast conventional method |
| Gram volume (mAh/g) | 135 | 141 | 128 |
The detection method of the gram volume of described dry linting amount and LiFePO4 is as follows.
(1) dry linting rate method of testing: select the positive plate being just coated with to shake gently, remove pole piece surface powder, then weigh for 100, be designated as G1, after corresponding LiFePO4 pole piece coiling completes, then take respectively it apart gently shake, remove pole piece surface powder, then weigh, be designated as G2, dry linting rate=G2/G1 × 100%.
(2) gram volume detection method: first record the weight of pole piece in each battery and calculate LiFePO
4the weight of/SiC active material, treats that battery obtains the capacity of whole battery on BK7064 (10A) type formation cabinet after forming and capacity dividing, and the weight by battery capacity divided by its active material, just obtains gram volume.
From table 1 and table 2, with conventional method comparison, pole piece dry linting phenomenon has reduced greatly; Its gram volume also can improve 5.5%-10.16%.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the amendment done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (1)
1. LiFePO is prepared in a microwave heating
4the method of/SiC positive plate of lithium battery, is characterized in that, comprises the following steps:
(1) by common commercially available LiFePO
4be placed in mass concentration and be 30% Li
2cO
3in solution, soak 3h, and fully stir, solution moisture content testing is evaporated;
(2) by the LiFePO after soaking
4roasting 5h at 500 DEG C;
(3) at the LiFePO through roasting gained
4in powder, add with respect to LiFePO
4the content of positive active material is that the particle diameter of 10wt% is the SiC of 150 μ m, the mixture obtaining is heated in microwave oven, microwave power is adjusted to 500W, control time is 10 minutes, again with mixed preparing form slurry such as binding agent, conductive agent, additive, solvents, through being coated with, being dried, roll film, cutting, be made into LiFePO
4/ SiC positive plate of lithium battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210094656.5A CN102664247B (en) | 2012-04-01 | 2012-04-01 | Method for preparing LiFePO4/SiC lithium battery positive plate by microwave heating |
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|---|---|---|---|
| CN201210094656.5A CN102664247B (en) | 2012-04-01 | 2012-04-01 | Method for preparing LiFePO4/SiC lithium battery positive plate by microwave heating |
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| CN102664247B true CN102664247B (en) | 2014-09-03 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103390750B (en) * | 2013-07-26 | 2015-08-05 | 合肥国轩高科动力能源股份公司 | A kind of preparation method of lithium iron phosphate positive material |
| CN104600300B (en) * | 2015-01-09 | 2017-04-12 | 贵州中伟正源新材料有限公司 | Method for preparing silicon carbide coated zinc oxalate negative material |
| CN105118969B (en) * | 2015-10-08 | 2017-06-23 | 清华大学深圳研究生院 | A kind of preparation method for improving lithium iron phosphate positive material high rate performance |
| CN105609716A (en) * | 2015-12-21 | 2016-05-25 | 宁波高新区锦众信息科技有限公司 | Preparation method for carbon-silicon coated lithium iron phosphate composite material for lithium ion battery |
| CN105514380A (en) * | 2015-12-21 | 2016-04-20 | 宁波高新区锦众信息科技有限公司 | Preparation method of LiFeSiO composite material for Li-ion batteries |
| CN106410137A (en) * | 2016-09-30 | 2017-02-15 | 江苏翔鹰新能源科技有限公司 | Nanometer silicon carbide coated lithium nickel manganese cobalt cathode material and preparation method thereof |
| CN114613944B (en) * | 2022-03-25 | 2023-11-21 | 华侨大学 | A method of preparing solid-state battery electrodes through microwave technology |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1767238A (en) * | 2005-11-15 | 2006-05-03 | 厦门大学 | Lithium iron phosphate cathode material and preparation method thereof |
| CN101217195A (en) * | 2007-12-28 | 2008-07-09 | 龚思源 | A lithium ion battery anode material of lithium iron phosphate and the corresponding vapor deposition and cladding method of conductive network |
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| US7781100B2 (en) * | 2005-05-10 | 2010-08-24 | Advanced Lithium Electrochemistry Co., Ltd | Cathode material for manufacturing rechargeable battery |
| US9391315B2 (en) * | 2010-04-23 | 2016-07-12 | Panasonic Intellectual Property Management Co., Ltd. | Negative electrode for lithium ion battery and method for producing the same, and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1767238A (en) * | 2005-11-15 | 2006-05-03 | 厦门大学 | Lithium iron phosphate cathode material and preparation method thereof |
| CN101217195A (en) * | 2007-12-28 | 2008-07-09 | 龚思源 | A lithium ion battery anode material of lithium iron phosphate and the corresponding vapor deposition and cladding method of conductive network |
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