CN101118978A - Lithium ion battery with FePO4/LixCn as electrode couple and method for making same - Google Patents
Lithium ion battery with FePO4/LixCn as electrode couple and method for making same Download PDFInfo
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- CN101118978A CN101118978A CNA2006100891196A CN200610089119A CN101118978A CN 101118978 A CN101118978 A CN 101118978A CN A2006100891196 A CNA2006100891196 A CN A2006100891196A CN 200610089119 A CN200610089119 A CN 200610089119A CN 101118978 A CN101118978 A CN 101118978A
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- lithium ion
- lixcn
- fepo
- ion battery
- battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 present invention discloses a lithium ion battery taking FePo4/LixCn as electrode couple as well as the preparing method therein, belonging to the field of energy technology. The present invention is characterized in that the lithium ion battery takes FePo4 as the material of the anode for the battery, and LixCn as the cathode material for the battery. The present invention also takes Liquid paraffin, n-dodecane, tetrahydrofuran and polyethylene glycol oxide as the protecting agents. An environmental protecting type FePO4 material is chosen as the material for the anode of the lithium ion battery. The phosphoric acid KTX includes a heterosite structure, the undefined structure, the monocline and the rhombic system structure; wherein, the heterosite structure and the undefined structure have high specific capacity. Through adopting the LixCn protecting agent, the cathode material of LixCn can be easily assembled into the battery, and thus a lithium free anode material FePO4 can be successively applied into the lithium ion battery. The assembled battery can reach a first electric discharging capacity of 122mAh per gram(FePO4) under the current density of 0.1mA per cm2.
Description
Technical field
The invention belongs to the energy and material technical field, particularly a kind of with FePO
4/ Li
xC
nBe new type lithium ion battery of electrode pair and preparation method thereof.
Background technology
Continually developing of new forms of energy is the important foundation of human social.Along with the progress of science and technology, people are more and more strong to the demand of the removable energy, particularly the demand of pure electric vehicle constantly strengthened with the aggravation of oil and environmental crisis.Can the secondary chemical sources of electric energy technology that break through inexpensive, safety, environmental friendliness, excellent performance at present be the bottleneck of the pure electric vehicle development of restriction.
Lithium ion battery has been considered to the choosing of the ideal of high power capacity high power battery because of its high-energy-density, excellent cycle performance and retention of charge since coming out the beginning of the nineties in last century.At present, the positive and negative pole material that is mainly used in lithium ion battery is embedding lithium transition-metal oxide and carbon (graphite), and the former mainly uses stratiform LiCoO
2, this material is used widely in compact battery, but except the restraining factors of cobalt resource, it overcharges insecurity and has determined it not to be applied in high capacity cell.People expect that spinelle LiMn2O4 can be with its inexpensive and relative LiCoO
2The advantage of safety plays a role in high capacity cell, but the solution that does not always find at its capacity shortcoming low and the high temperature cyclic performance difference, so still can not in actual battery, promote.Therefore, seek the ideal electrode active material of lithium ion battery from resource, environmental protection and security performance aspect, be still the research focus of quite a while World chemical power supply circle from now on and develop the key of pure electric vehicle.
Consider from resource and environmental, be accompanied by the appearance of lithium ion battery, iron system is anodal just to be that people expect for LiCoO always
2Alternative materials.LiFeO to stratiform
2Many deep researchs are arranged, but because Fe
4+/ Fe
3+Fermi energy level and Li that electricity is right
+Being separated by of/Li is too far away, and Fe
3+/ Fe
2+The electricity to again with Li
+Being separated by of/Li is too near, simultaneously, and Fe
3+Ionic radius and Li
+The ratio of radius does not meet structural requirement, so, the LiFeO that has significant practical applications
2Research never has big progress.
FePO
4Be LiFePO
4Take off the lithium product, in the whole charging and discharging process with LiFePO
4Coexistence, this is FePO
4As electrode material report the earliest.FePO
4Have multiple different structure, closely related with its synthetic method.The FePO of different structure
4Has different electrochemical properties.Up to the present, FePO
4Electrode material does not also obtain industrial widespread usage, but that it has is cheap, abundant raw material, nontoxic, again high theoretical specific capacity and suitable voltage are arranged, be the positive electrode that gets a good chance of becoming the environmental type lithium ion battery.
If with FePO
4Be positive electrode, the lithium source can only come from negative pole, but lithium metal or lithium alloy all can't solve the Li dendrite problem.LixCn is proposed the nineties by Sony the earliest, has invented lithium ion battery, and the lithium source is to be provided by positive pole, thereby has solved LixCn unstable problems such as coating difficulty of bringing in air.And we have found the protective agent of LixCn in this patent, cause FePO
4/ LixCn new type lithium ion battery can be successfully applied to industrial.
Summary of the invention
The object of the present invention is to provide a kind of with FePO
4/ LixCn is new type lithium ion battery of electrode pair and preparation method thereof.
The a kind of of the present invention's proposition is the lithium ion battery of electrode pair with FePO4/LixCn, and it is characterized in that: described lithium ion battery is with FePO
4Be positive electrode, with Li
xC
nBe negative material, with liquid paraffin, n-dodecane, oxolane, polyethylene glycol oxide are protective agent.
It is a kind of with FePO that the present invention proposes
4/ LixCn is the preparation method of the lithium ion battery of electrode pair, it is characterized in that: described method is carried out according to following steps:
(1) with the Fe (NO of 0.1mol/L
3)
3The H of solution and 0.1mol/L
3PO
4The solution equal-volume mixes, and stirs and regulates pH to 7.0 with ammoniacal liquor, continues to be stirred to complete reaction, filters out sediment and with distilled water and ethanol cyclic washing, drying obtains FePO
42H
2The O solid;
(2) FePO that step 1 is obtained
42H
2O calcines down at 300 ℃ and got FePO in 3 hours
4Positive electrode;
(3) in the glove box of argon shield, Delanium and lithium powder are put into ball grinder by 3: 1 (mol ratio), add a small amount of n-dodecane and steel ball again, from glove box, take out and put into planetary ball mill, ball milling obtains lithium-graphite intercalation compound Li
xC
n
(4) take by weighing lithium-graphite intercalation compound Li respectively with 80: 10: 10 mass ratio
xC
n: acetylene black: polytetrafluoroethylene, make electrode after the grinding evenly;
(5) to be dissolved in the 1mol/L LiPF in ethyl carbonate+dimethyl carbonate (volume ratio is 1: 1) mixed solvent
6Be electrolyte, microporous polypropylene membrane is a barrier film, is assembled into battery;
It is a kind of with FePO that the present invention proposes
4/ LixCn is the preparation method of the lithium ion battery of electrode pair, it is characterized in that: described method is carried out according to following steps:
(1) with iron powder and NH
4H
2PO
4Be raw material, with iron powder and NH
4H
2PO
4Add in the entry by 1: 1 (mol ratio), at room temperature stir, and dry under 95 ℃, sample is handled in 600 ℃ Muffle furnace, in planetary ball mill, grind jointly then with 15% conductive agent acetylene carbon black, carry out smear again;
(2) with graphite, the conductive agent carbon black, adhesive PVDF, (90: 2: 8) are mixed in the N-methyl pyrrolidone and are coated with on Copper Foil by a certain percentage, and very anodal with this, the lithium sheet is a negative pole, in the lithium-ion electrolyte pond, carries out low discharging current;
(3) with protective agent the LixCn electrode is protected;
(4) used FePO
4Be the full battery of positive electrode assembling lithium ion.
Of the present invention with FePO
4/ LixCn is the new type lithium ion battery of electrode pair, has the following advantages:
● with new green environment protection type FePO
4Material is an anode material for lithium-ion batteries, and high ferric phosphate comprises structures such as heterosite structure, undefined structure, monocline and rhombic system, and wherein heterosite structure and undefined structure have higher specific capacity.
● with Li
xC
nBe successfully applied to lithium ion battery negative material; proposing graphite by Sony the earliest can reversible insertion lithium ion; character was very active after but lithium ion inserted graphite in advance; can't assembled battery; make lithium ion to provide by positive pole; negative pole is pure graphite, both present general lithium ion battery. and we have found several suitable Li
xC
nProtective agent makes Li
xC
nNegative material can success be assembled in the battery, this also makes no lithium anode material FePO
4Can successful being applied in the lithium ion battery.
Description of drawings
Fig. 1 is by the prepared high ferric phosphate (FePO of embodiment 2
4) (Cu target K alpha ray, λ=0.104056nm), embodiment 1 prepared high ferric phosphate is amorphous for the crystallogram of material.
Fig. 2 is by the prepared lithium-graphite intercalation compound (Li of embodiment 1
xC
n) crystallogram.(Cu target K alpha ray, λ=0.104056nm).
Fig. 3 is by the prepared FePO of embodiment 1
4, the assembled battery of LixCn material discharge curve first.
Fig. 4 is by the prepared FePO of embodiment 1
4, the cycle performance figure of LixCn material assembled battery under different current densities
Embodiment
Below in conjunction with embodiment skill scheme of the present invention is described further:
Embodiment 1
Fe (NO with 0.1mol/L
3)
3The H of solution and 0.1mol/L
3PO
4The solution equal-volume mixes, and stirs and regulates pH to 7.0 with ammoniacal liquor, continues to be stirred to complete reaction, filters out sediment and with distilled water and ethanol cyclic washing, dry 10h obtains FePO
42H
2The O solid is with FePO
42H
2O calcines down at 300 ℃ and got FePO in 3 hours
4
In the glove box of argon shield, 2.4 gram Delaniums (40um) and 0.28 gram lithium powder (100um) are put into the 50ml ball grinder, add 3cm again
3N-dodecane and 100g steel ball (3mm) take out from glove box and put into planetary ball mill, with the speed ball milling 12h of 200 commentaries on classics/min.
The XRD spectra of the gained LixCn that surveys is seen Fig. 2, and the reference standard card is lithium-graphite intercalation compound.
Make electrode as follows with two kinds of materials that embodiment 1 obtains.
Take by weighing the composite material of embodiment 1 gained respectively with 80: 10: 10 mass ratioes: acetylene black: polytetrafluoroethylene, make electrode after the grinding evenly, to be dissolved in the 1mol/L LiPF in ethyl carbonate+dimethyl carbonate (volume ratio is 1: 1) mixed solvent
6Be electrolyte, microporous polypropylene membrane is a barrier film, being assembled into simulated battery. Fig. 3 is the first charge-discharge curve of respective battery when the 4.2-2.5V cut-ff voltage, show that measured battery has the charging/discharging voltage platform about 3.2V, the reversible specific capacity that can calculate embodiment 1 positive electrode is about 100mAh/g. Fig. 4 is the cycle performance under the different current densities, and 100 weeks circulations back reversible capacities still reach more than 80% of initial capacity. in following examples similarly.
Embodiment 2
With iron powder and NH
4H
2PO
4Be raw material. with the NH of 5.6g iron powder and 11.2g
4H
2PO
4Add in the entry, at room temperature stir 5h, and dry 10h. handles 24h (in the air) with sample in 600 ℃ Muffle furnace under 95 ℃. in planetary ball mill, grind 24h jointly then, carry out smear again with 15% conductive agent acetylene carbon black.
With graphite; the conductive agent carbon black; adhesive PVDF is mixed in the N-methyl pyrrolidone by a certain percentage and is coated with on Copper Foil, and is very anodal with this; the lithium sheet is a negative pole; in the lithium-ion electrolyte pond, carry out low discharging current, use protective agent that we mention (as n-dodecane then; oxolane, polyethylene glycol oxide etc.) the LixCn electrode is protected.N-dodecane, oxolane vacuumize before fluid injection and can take away, and polyethylene glycol oxide can be dissolved in the electrolyte rapidly, and battery performance is had no effect.
With quadrat method assembling simulated battery, at 0.1mA/cm
2Under the current density first discharge capacity can reach 122mAh/g (FePO
4).
Claims (3)
1. one kind is the lithium ion battery of electrode pair with FePO4/LixCn, and it is characterized in that: described lithium ion battery is with FePO
4Be positive electrode, with Li
xC
nBe negative material, with liquid paraffin, n-dodecane, oxolane, polyethylene glycol oxide are protective agent, (wherein x/n=0.1-0.33).
2. one kind with FePO
4/ LixCn is the preparation method of the lithium ion battery of electrode pair, it is characterized in that: described method is carried out according to following steps:
(1) with the Fe (NO of 0.1mol/L
3)
3The H of solution and 0.1mol/L
3PO
4The solution equal-volume mixes, and stirs and regulates pH to 7.0 with ammoniacal liquor, continues to be stirred to complete reaction, filters out sediment and with distilled water and ethanol cyclic washing, drying obtains FePO
42H
2The O solid;
(2) FePO that step 1 is obtained
42H
2O calcines down at 300 ℃ and got FePO in 3 hours
4Positive electrode;
(3) in the glove box of argon shield, Delanium and lithium powder are put into ball grinder by 3: 1 (mol ratio), add a spot of n-dodecane and steel ball again, from glove box, take out and put into planetary ball mill, ball milling obtains lithium-graphite intercalation compound Li
xC
n
(4) take by weighing lithium-graphite intercalation compound Li respectively with 80: 10: 10 mass ratio
xC
n: acetylene black: polytetrafluoroethylene, make electrode after the grinding evenly;
(5) to be dissolved in the 1mol/L LiPF in ethyl carbonate+dimethyl carbonate (volume ratio is 1: 1) mixed solvent
6Be electrolyte, microporous polypropylene membrane is a barrier film, is assembled into battery.
3. one kind with FePO
4/ LixCn is the preparation method of the lithium ion battery of electrode pair, it is characterized in that: described method can also be carried out according to following steps:
(1) with iron powder and NH
4H
2PO
4Be raw material, with iron powder and NH
4H
2PO
4Add in the entry by 1: 1 (mol ratio), at room temperature stir, and dry under 95 ℃, sample is handled in 600 ℃ Muffle furnace, in planetary ball mill, grind jointly then with 15% conductive agent acetylene carbon black, carry out smear again;
(2) with graphite, the conductive agent carbon black, adhesive PVDF, (90: 2: 8) are mixed in the N-methyl pyrrolidone and are coated with on Copper Foil by a certain percentage, and very anodal with this, the lithium sheet is a negative pole, in the lithium-ion electrolyte pond, carries out low discharging current;
(3) with protective agent the LixCn electrode is protected;
(4) used FePO
4Be the full battery of positive electrode assembling lithium ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100891196A CN101118978A (en) | 2006-08-04 | 2006-08-04 | Lithium ion battery with FePO4/LixCn as electrode couple and method for making same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100891196A CN101118978A (en) | 2006-08-04 | 2006-08-04 | Lithium ion battery with FePO4/LixCn as electrode couple and method for making same |
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|---|---|
| CN101118978A true CN101118978A (en) | 2008-02-06 |
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ID=39054983
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|---|---|---|---|
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|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101841039A (en) * | 2010-04-29 | 2010-09-22 | 上海电力学院 | Cathode material ferric phosphate doped with metallic ions for lithium ion battery and preparation method thereof |
| CN102867983A (en) * | 2011-07-04 | 2013-01-09 | 中国人民解放军63971部队 | Nonaqueous secondary lithium battery |
| CN103915626A (en) * | 2014-04-21 | 2014-07-09 | 上海电力学院 | Sodium ion battery composite positive material and preparation method thereof |
| CN104600308A (en) * | 2015-01-20 | 2015-05-06 | 浙江大学 | Lithium ion battery negative electrode material and method for preparing membrane electrode thereof |
| CN101789506B (en) * | 2009-01-22 | 2015-11-25 | 中国科学院上海硅酸盐研究所 | Composite cathode material for lithium ion battery and preparation method |
| CN108598422A (en) * | 2012-03-28 | 2018-09-28 | 株式会社东芝 | Electrode, nonaqueous electrolyte battery, battery pack and vehicle |
| CN109686921A (en) * | 2018-11-21 | 2019-04-26 | 清华大学 | A kind of composition metal cathode of lithium and preparation method thereof with lithium carbon compound interface layer |
| CN115092930A (en) * | 2022-06-23 | 2022-09-23 | 北京航空航天大学 | K x C y Preparation method of battery cathode material, battery cathode material and battery |
| CN115159852A (en) * | 2022-05-25 | 2022-10-11 | 齐鲁工业大学 | Preparation method and application of iron phosphate microcrystalline glass electrode material |
-
2006
- 2006-08-04 CN CNA2006100891196A patent/CN101118978A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101789506B (en) * | 2009-01-22 | 2015-11-25 | 中国科学院上海硅酸盐研究所 | Composite cathode material for lithium ion battery and preparation method |
| CN101841039A (en) * | 2010-04-29 | 2010-09-22 | 上海电力学院 | Cathode material ferric phosphate doped with metallic ions for lithium ion battery and preparation method thereof |
| CN102867983A (en) * | 2011-07-04 | 2013-01-09 | 中国人民解放军63971部队 | Nonaqueous secondary lithium battery |
| CN108598422A (en) * | 2012-03-28 | 2018-09-28 | 株式会社东芝 | Electrode, nonaqueous electrolyte battery, battery pack and vehicle |
| CN103915626A (en) * | 2014-04-21 | 2014-07-09 | 上海电力学院 | Sodium ion battery composite positive material and preparation method thereof |
| CN104600308A (en) * | 2015-01-20 | 2015-05-06 | 浙江大学 | Lithium ion battery negative electrode material and method for preparing membrane electrode thereof |
| CN104600308B (en) * | 2015-01-20 | 2017-04-12 | 浙江大学 | Lithium ion battery negative electrode material and method for preparing membrane electrode thereof |
| CN109686921A (en) * | 2018-11-21 | 2019-04-26 | 清华大学 | A kind of composition metal cathode of lithium and preparation method thereof with lithium carbon compound interface layer |
| CN115159852A (en) * | 2022-05-25 | 2022-10-11 | 齐鲁工业大学 | Preparation method and application of iron phosphate microcrystalline glass electrode material |
| CN115159852B (en) * | 2022-05-25 | 2023-10-03 | 齐鲁工业大学 | Preparation method and application of iron phosphate microcrystalline glass electrode material |
| CN115092930A (en) * | 2022-06-23 | 2022-09-23 | 北京航空航天大学 | K x C y Preparation method of battery cathode material, battery cathode material and battery |
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Application publication date: 20080206 |