CN103378354A - Negative active material composition and lithium iron phosphate battery comprising same - Google Patents
Negative active material composition and lithium iron phosphate battery comprising same Download PDFInfo
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- CN103378354A CN103378354A CN2012101287067A CN201210128706A CN103378354A CN 103378354 A CN103378354 A CN 103378354A CN 2012101287067 A CN2012101287067 A CN 2012101287067A CN 201210128706 A CN201210128706 A CN 201210128706A CN 103378354 A CN103378354 A CN 103378354A
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- active material
- hard carbon
- negative electrode
- electrode active
- feed composition
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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
- 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
Abstract
The invention relates to a negative active material composition and a lithium iron phosphate battery comprising the same. The negative active material composition comprises hard carbon and graphite, wherein the mass percentage of the hard carbon is 0.1 to 50 percent, a positive electrode is made of an olivine lithium iron phosphate material, the graphite and the hard carbon material form the negative electrode, and the negative electrode is matched with the lithium iron phosphate positive electrode with high safety, so that the lithium iron phosphate battery has excellent large-rate charging-discharging performance, low-temperature discharging performance, safety performance and high volume energy density; moreover, by integrating the characteristics of a charging-discharging platform curve of the hard carbon, the discharging platform of the lithium iron phosphate is enabled not to be too flat, the monitoring of a battery BMS (battery management system) on the voltage of the battery can be favored, and the negative active material composition can be widely applied to the lithium iron phosphate battery and particularly applied to the power-type lithium iron phosphate battery.
Description
Technical field
The present invention relates to a kind of ferric phosphate lithium cell, more particularly, relate to a kind of ferric phosphate lithium cell that contains the negative electrode active material feed composition.
Background technology
Lithium ion battery is the green battery of a new generation, is considered to 21st century has significant impact power to the people's economic life new high-tech product.Lithium ion battery has that volume energy density is large, voltage is high, pollution-free, the advantage such as discharge is little, thereby used more and more extensively; Ferric phosphate lithium cell is considered to the most potential minitype motivation instrument that applies to, the lithium ion battery of new generation of pure electric vehicle, and it does not contain precious metal, and raw material sources are abundant, and Stability Analysis of Structures has very high security performance.With graphite negative electrodes coupling charging/discharging voltage and steady, the voltage platform of moderate (3.4V) is arranged; But LiFePO4 and graphitic carbon negative pole have following shortcoming: the first, and the conductivity of LiFePO 4 material own is low, causes high-rate discharge ability relatively poor; The second, poor performance at low temperatures, LiFePO4 and graphite-like low-temperature conductivity reduce, and graphite negative electrodes is embedding lithium Speed Reduction at low temperatures, causes easily the charging difficulty, causes analysing the lithium phenomenon; The 3rd, LiFePO4 and graphitic carbon negative discharge platform and steady cause power-supply management system BMS to be difficult to accurate monitoring, have increased ferric phosphate lithium cell combination difficulty or have raised the combination cost.These shortcomings have hindered applying in the electrokinetic cell on a large scale of ferric phosphate lithium cell.
Summary of the invention
The technical problem to be solved in the present invention is, for the defects of prior art, provides a kind of negative electrode active material feed composition.
The technical solution adopted for the present invention to solve the technical problems is: construct a kind of negative electrode active material feed composition.
In a kind of negative electrode active material feed composition of the present invention, comprise hard carbon and graphite in the described negative electrode active material feed composition, the mass percent of wherein said hard carbon is 0.1～50%.
In a kind of negative electrode active material feed composition of the present invention, described graphite comprises one or more in native graphite, Delanium, the soft carbon.
In a kind of negative electrode active material feed composition of the present invention, described hard carbon comprises at least a in resinae hard carbon, plant hard carbon, the pitch class hard carbon.
In a kind of negative electrode active material feed composition of the present invention, described hard carbon also can be the hard carbon after the carbon layer on surface modification.
In a kind of negative electrode active material feed composition of the present invention, the anabolic process of described negative electrode active material feed composition occurs in the premixed of the front described graphite of batching and described hard carbon.
In a kind of negative electrode active material feed composition of the present invention, described graphite and described hard carbon mixed when the anabolic process of described negative electrode active material feed composition occurred in batching.
In a kind of negative electrode active material feed composition of the present invention, the average grain diameter of described negative active core-shell material composition grain is 2～60 microns, and specific area is 2.0～30.0 meters squared per gram.
The technical problem to be solved in the present invention is, for the defects of prior art, provides a kind of ferric phosphate lithium cell.
The technical solution adopted for the present invention to solve the technical problems is: construct a kind of ferric phosphate lithium cell.
In a kind of ferric phosphate lithium cell of the present invention, comprising:
The negative electrode active material feed composition comprises hard carbon and graphite in the described negative electrode active material feed composition, and the mass percent of wherein said hard carbon is 0.1～50%;
Anodal LiFePO 4 material will be coated on the aluminium foil that scribbles conductive carbon layer after the slurrying of described anodal LiFePO 4 material process batching;
Described ferric phosphate lithium cell is by making the rolling core with described positive and negative pole material, and through baking, fluid injection, change into, obtain behind the partial volume.
In a kind of ferric phosphate lithium cell of the present invention, described anodal LiFePO 4 material average grain diameter is 0.1～10 micron, and specific area is 5～20 meters squared per gram.
In a kind of ferric phosphate lithium cell of the present invention, described aluminum foil thickness is 8～25 microns, and conduction carbon coating thickness is 0～10 micron.
Implement a kind of negative electrode active material feed composition of the present invention and contain the ferric phosphate lithium cell of said composition, has following beneficial effect: the battery of the present invention by adopting negative active core-shell material combination and the aluminium foil LiFePO4 that conductive carbon layer is arranged to be combined into, have good high-rate discharge ability, preferably low temperature discharge and recharge, and moderate voltage platform curve, overcome the defective of general ferric phosphate lithium cell, improved the performance of LiFePO4, made better to apply in the middle of the electrokinetic cell.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Get pure Delanium and hard carbon in the ball milling in-tank mixing, both mass ratioes are 99.9: 0.1, and are for subsequent use; Get 1.5% binding agent CMC and be dissolved in the deionized water, add 1% conductive agent SUPER-P and in the double-planet mixer, disperseed 2 hours, add the mixture of 95% Delanium that mixes and hard carbon, in the double-planet mixer, continue after vacuumizing to stir 6 hours; Add afterwards 2.5% binding agent SBR, stir after 0.5 hour, be coated with at coating machine, through colding pressing, obtain required negative plate after the cut-parts.
Get 16 micron aluminum foils in the two-sided 4 microns conductive carbon layer of letterpress spraying one deck single face 2 micron thickness, dry for standby; After being averaged particle diameter and being 1.52 microns nano-grade lithium iron phosphate batching, be coated on the aluminium foil that contains conductive carbon layer, through colding pressing, obtain required positive plate after the cut-parts.
Gained positive/negative plate routinely technique is reeled, baking, fluid injection, is changed into, obtains ferric phosphate lithium cell behind the partial volume.With reference to GB GB/T18287-2000 battery is carried out electrochemical property test and low-temperature test.Test result is as shown in table 1.
Embodiment 2
Get pure Delanium and hard carbon in the ball milling in-tank mixing, both mass ratioes are 85: 15, and are for subsequent use; Get 1.5% binding agent CMC and be dissolved in the deionized water, add 1% conductive agent SUPER-P and in the double-planet mixer, disperseed 2 hours, add the mixture of 95% Delanium that mixes and hard carbon, in the double-planet mixer, continue after vacuumizing to stir 6 hours; Add afterwards 2.5% binding agent SBR, stir after 0.5 hour, be coated with at coating machine, through colding pressing, obtain required negative plate after the cut-parts.
Get 16 micron aluminum foils in the two-sided 4 microns conductive carbon layer of letterpress spraying one deck single face 2 micron thickness, dry for standby; After being averaged particle diameter and being 1.52 microns nano-grade lithium iron phosphate batching, be coated on the aluminium foil that contains conductive carbon layer, through colding pressing, obtain required positive plate after the cut-parts.
Gained positive/negative plate routinely technique is reeled, baking, fluid injection, is changed into, obtains ferric phosphate lithium cell behind the partial volume.With reference to GB GB/T18287-2000 battery is carried out electrochemical property test and low-temperature test.Test result is as shown in table 1.
Embodiment 3
Get pure Delanium and hard carbon in the ball milling in-tank mixing, both mass ratioes are 65: 35, and are for subsequent use; Get 1.5% binding agent CMC and be dissolved in the deionized water, add 1% conductive agent VGCF and in the double-planet mixer, disperseed 2 hours, add the mixture of 95% Delanium that mixes and hard carbon, in the double-planet mixer, continue after vacuumizing to stir 6 hours; Add afterwards 2.5% binding agent SBR, stir after 0.5 hour, be coated with at coating machine, through colding pressing, obtain required negative plate after the cut-parts.It is identical with real row 1 that positive plate and battery are made, and gained positive/negative plate routinely technique is reeled, baking, fluid injection, changed into, obtains ferric phosphate lithium cell behind the partial volume.The method of performance test is identical with embodiment 1 with condition, and test result is as shown in table 1.
Embodiment 4
Get pure Delanium and hard carbon in the ball milling in-tank mixing, both mass ratioes are 50: 50, and are for subsequent use; Get 1.5% binding agent CMC and be dissolved in the deionized water, add 1% conductive agent VGCF and in the double-planet mixer, disperseed 2 hours, add the mixture of 95% Delanium that mixes and hard carbon, in the double-planet mixer, continue after vacuumizing to stir 6 hours; Add afterwards 2.5% binding agent SBR, stir after 0.5 hour, be coated with at coating machine, through colding pressing, obtain required negative plate after the cut-parts.It is identical with real row 1 that positive plate and battery are made, and gained positive/negative plate routinely technique is reeled, baking, fluid injection, changed into, obtains ferric phosphate lithium cell behind the partial volume.The method of performance test is identical with embodiment 1 with condition, and test result is as shown in table 1.
Embodiment 5
The making of negative plate is identical with embodiment 2.
Get 16 micron aluminum foils in the two-sided 6 microns conductive carbon layer of letterpress spraying one deck single face 3 micron thickness, dry for standby; After being averaged particle diameter and being 3.5 microns nano-grade lithium iron phosphate batching, be coated on the aluminium foil that contains conductive carbon layer, through colding pressing, obtain required positive plate after the cut-parts.
Gained positive/negative plate routinely technique is reeled, baking, fluid injection, is changed into, obtains ferric phosphate lithium cell behind the partial volume.The method of performance test is identical with embodiment 1 with condition, and test result is as shown in table 1.
Embodiment 6
Get Delanium, native graphite and hard carbon in the ball milling in-tank mixing, both mass ratioes are 50: 35: 15, and are for subsequent use; Get 1.5% binding agent CMC and be dissolved in the deionized water, add 1% conductive agent SUPER-P and in the double-planet mixer, disperseed 2 hours, add the mixture of 95% Delanium that mixes and hard carbon, in the double-planet mixer, continue after vacuumizing to stir 6 hours; Add afterwards 2.5% binding agent SBR, stir after 0.5 hour, be coated with at coating machine, through colding pressing, obtain required negative plate after the cut-parts.Positive plate and battery are made identical with embodiment 1.
Gained positive/negative plate routinely technique is reeled, baking, fluid injection, is changed into, obtains ferric phosphate lithium cell behind the partial volume.The method of performance test is identical with embodiment 1 with condition, and test result is as shown in table 1.
Embodiment 7
Getting 1.5% binding agent CMC is dissolved in the deionized water, adding 1% conductive agent SUPER-P disperseed 2 hours in the double-planet mixer, the Delanium of weighing 95% and hard carbon cathode, the mass ratio of Delanium and hard carbon is 85: 15, continues after vacuumizing to stir 6 hours in the double-planet mixer; Add afterwards 2.5% binding agent SBR, stir after 1 hour, be coated with at coating machine, through colding pressing, obtain required negative plate after the cut-parts.
Get 16 micron aluminum foils in the two-sided 4 microns conductive carbon layer of letterpress spraying one deck single face 2 micron thickness, dry for standby; After being averaged particle diameter and being 3.5 microns nano-grade lithium iron phosphate batching, be coated on the aluminium foil that contains conductive carbon layer, through colding pressing, obtain required positive plate after the cut-parts.
Gained positive/negative plate routinely technique is reeled, baking, fluid injection, is changed into, obtains ferric phosphate lithium cell behind the partial volume.The method of performance test is identical with embodiment 1 with condition, and test result is as shown in table 1.
Comparative Examples 1
It is for subsequent use to get pure Delanium, and all the other manufacture methods are identical with embodiment 2, and the method for performance test is identical with embodiment 1 with condition, and test result is as shown in table 1.
Comparative Examples 2
The preparation of negative plate is identical with Comparative Examples 1, the preparation of the positive plate positive pole aluminium foil that do not coexist is not coated with the conductive carbon layer of 2 microns two-sided 4 micron thickness of single face, all the other experimentations are identical, and the method for performance test is identical with embodiment 1 with condition, and test result is as shown in table 1.
Can find out a kind of negative electrode active material feed composition of the present invention and contain the ferric phosphate lithium cell of said composition by above embodiment, the battery of the present invention by adopting negative active core-shell material combination and the aluminium foil LiFePO4 that conductive carbon layer is arranged to be combined into, have good high-rate discharge ability, preferably low temperature discharge and recharge, and moderate voltage platform curve, overcome the defective of general ferric phosphate lithium cell, improved the performance of LiFePO4, made better to apply in the middle of the electrokinetic cell.
Although by above embodiment the present invention is disclosed, protection scope of the present invention is not limited to this, is not departing under the condition of the present invention design, and the distortion that above each member is done, replacement etc. all will fall in the claim scope of the present invention.
Claims (10)
1. a negative electrode active material feed composition is characterized in that, comprises hard carbon and graphite in the described negative electrode active material feed composition, and the mass percent of wherein said hard carbon is 0.1～50%.
2. negative electrode active material feed composition according to claim 1 is characterized in that, described graphite comprises one or more in native graphite, Delanium, the soft carbon.
3. negative electrode active material feed composition according to claim 1 is characterized in that, described hard carbon comprises at least a in resinae hard carbon, plant hard carbon, the pitch class hard carbon.
4. negative electrode active material feed composition according to claim 1 is characterized in that, described hard carbon also can be the hard carbon after the carbon layer on surface modification.
5. negative electrode active material feed composition according to claim 1 is characterized in that, the anabolic process of described negative electrode active material feed composition occurs in the premixed of the front described graphite of batching and described hard carbon.
6. negative electrode active material feed composition according to claim 1 is characterized in that, described graphite and described hard carbon mixed when the anabolic process of described negative electrode active material feed composition occurred in batching.
7. negative electrode active material feed composition according to claim 1 is characterized in that, the average grain diameter of described negative active core-shell material composition grain is 2～60 microns, and specific area is 2.0～30.0 meters squared per gram.
8. a ferric phosphate lithium cell is characterized in that, comprising:
The negative electrode active material feed composition comprises hard carbon and graphite in the described negative electrode active material feed composition, and the mass percent of wherein said hard carbon is 0.1～50%;
Anodal LiFePO 4 material will be coated on the aluminium foil that scribbles conductive carbon layer after the slurrying of described anodal LiFePO 4 material process batching;
Described ferric phosphate lithium cell is by making the rolling core with described positive and negative pole material, and through baking, fluid injection, change into, obtain behind the partial volume.
9. ferric phosphate lithium cell according to claim 8 is characterized in that, described anodal LiFePO 4 material average grain diameter is 0.1～10 micron, and specific area is 5～20 meters squared per gram.
10. ferric phosphate lithium cell according to claim 8 is characterized in that, described aluminum foil thickness is 8～25 microns, and conduction carbon coating thickness is 0～10 micron.
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| CN2012101287067A CN103378354A (en) | 2012-04-27 | 2012-04-27 | Negative active material composition and lithium iron phosphate battery comprising same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105810899A (en) * | 2016-03-10 | 2016-07-27 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery |
| CN108155381A (en) * | 2017-12-25 | 2018-06-12 | 北京国能电池科技有限公司 | Lithium cell cathode material, lithium ion battery suitable for start and stop power supply and preparation method thereof |
| CN108155379A (en) * | 2017-12-25 | 2018-06-12 | 北京国能电池科技有限公司 | Lithium ion battery suitable for low temperature environment and preparation method thereof |
| CN110277543A (en) * | 2018-03-16 | 2019-09-24 | 国家能源投资集团有限责任公司 | Mix negative electrode material and cathode pole piece and preparation method thereof |
| CN114883529A (en) * | 2022-07-06 | 2022-08-09 | 天能新能源(湖州)有限公司 | Low-temperature starting lithium ion battery |
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| CN101840787A (en) * | 2010-05-18 | 2010-09-22 | 东莞新能源科技有限公司 | Method for manufacturing positive pole plate of lithium-ion capacitor and lithium-ion capacitor using same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105810899A (en) * | 2016-03-10 | 2016-07-27 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery |
| CN108155381A (en) * | 2017-12-25 | 2018-06-12 | 北京国能电池科技有限公司 | Lithium cell cathode material, lithium ion battery suitable for start and stop power supply and preparation method thereof |
| CN108155379A (en) * | 2017-12-25 | 2018-06-12 | 北京国能电池科技有限公司 | Lithium ion battery suitable for low temperature environment and preparation method thereof |
| CN110277543A (en) * | 2018-03-16 | 2019-09-24 | 国家能源投资集团有限责任公司 | Mix negative electrode material and cathode pole piece and preparation method thereof |
| CN114883529A (en) * | 2022-07-06 | 2022-08-09 | 天能新能源(湖州)有限公司 | Low-temperature starting lithium ion battery |
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Application publication date: 20131030 |