CN102005615B - 可充电的镍离子电池 - Google Patents
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 42
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000011149 active material Substances 0.000 claims abstract description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007774 positive electrode material Substances 0.000 claims description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 7
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- 239000007773 negative electrode material Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical group [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 claims description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 15
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- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 10
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
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- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
本发明公开了一种可充电的镍离子电池,其正极采用镍离子能进行可逆脱嵌的锰的氧化物材料,负极采用以镍元素为主的活性材料,电解质采用以镍的可溶性盐为溶质水为溶剂并具有离子导电性的液态或凝胶态电解质,电解质的pH值介于3~7之间。该电池具有循环寿命长、容量高、安全、环保、成本低廉等特点,可广泛应用于消费电子、电动车、通讯、航空航天和军事等领域。
Description
技术领域
本发明属电池技术领域,具体涉及一种镍离子在正极活性材料脱嵌和在负极还原或氧化的可充电的镍离子电池。
背景技术
小型和可移动电池是人类现代生活的基石,每年全球电池的市场达1000亿美元以上,并带动相关产业如消费电子、电动车、通讯等领域的蓬勃发展。每一次新型电池的发明都可视为现代化学发展的里程碑,而且发明的电池可为人类服务长达上百年。
现在小型和可移动的电池主要有锌锰电池、镍氢电池、镍铬电池、锂离子电池、铅酸电池和锌离子电池这六种。其中锌锰电池主要为一次电池,不可重复充放电,其它电池为二次电池,可重复充放电。二次电池能充分利用原材料,故其更经济实用,但现存的二次电池循环寿命大多为几百次,因此使用一段时间后,需更换新的电池以确保放电时间不会缩短。
随着社会的进步,人类对电子产品的需求和要求也不断更新,电池的性能决定了电子产品所能达到的最高性能,发明同时具有高能量密度和长寿命的二次电池成为未来新型电子产品发展的先决条件,例如电动汽车需要长寿命的电池以符合汽车长达10年以上的使用寿命,同时这种电池还必须具有低成本、安全和环保的特点,以顺应未来“低碳”经济发展的大趋势。
发明内容
本发明的目的在于提出一种高容量、循环寿命长的二次电池。
锰的氧化物(Manganese Oxides,在本发明中简写为MNO),如二氧化锰、三氧化二锰、四氧化三锰等具有大尺寸的开放式结构,隧道中的阳离子可以和水溶液中的阳离子进行交换,即具有离子交换能力,在离子交换过程中,这些隧道结构可保持稳定。在研究中我们首次发现了二价镍离子(Ni2+)在锰的氧化物材料中可逆嵌入和脱出的行为,并伴随着Mn的可逆变价来储存和释放电子(电能),原理如式(1)所示:
这种镍离子的嵌入行为具有可逆程度好和循环次数多等特点,在此研究的基础之上,我们以可嵌镍离子的锰的氧化物为正极,以镍为负极,以含镍离子的电解液组成一种全新的镍离子电池,在充电时镍离子脱出锰的氧化物隧道经过电解液然后在负极沉积,放电时负极镍溶解为镍离子经过电解液嵌入到锰的氧化物正极材料的隧道中,因此可以把这种镍离子电池也比喻为摇椅电池,摇椅的两端为电池的正负极,而镍离子在摇椅的两端来回奔跑。
这种镍离子电池储存电子的机理如下:
负极:
在上述研究基础上,本发明提供的可充电的镍离子电池的具体方案如下:
一种可充电的镍离子电池,由正极、负极、介于两者之间的隔离膜以及含有阴阳离子并具有离子导电性的电解质组成,其中:所述负极采用以镍元素为主的活性材料;正极活性材料为可吸藏和释放镍离子的锰的氧化物材料;所述电解质是以镍的可溶性盐为溶质、水为溶剂并具有离子导电性的液态或凝胶态材料,pH值介于3~7之间。
构成正极活性材料的锰的氧化物优选二氧化锰、三氧化二锰或四氧化三锰。
所述负极可以是纯金属镍或镍的合金。
所述负极也可以采用如下方案:负极包括集流体和集流体上的以镍粉末为主的活性材料,该活性材料是用镍粉和粘结剂制成的膜状材料,其中粘结剂可选择聚四氟乙烯、水溶性橡胶、聚偏四氟乙烯或纤维素。进一步可在负极活性材料中添加缓腐剂,缓腐剂的添加量为负极膜质量的1%以下,缓腐剂用于抑止或消除镍元素析氢反应,所述缓腐剂可以采用铟的氧化物、或铟的氢氧化物。进一步还可在负极活性材料中添加电子导电剂,电子导电剂的添加量为负极膜质量的50%以下,优选石墨、碳黑、乙炔黑、炭纤维或炭纳米管。
所述镍的可溶性盐优选硝酸镍、硫酸镍或氯化镍。可通过添加酸、碱或缓冲溶液等来调节电解质的pH值在3~7。
本发明镍离子电池是利用镍离子(Ni2+)在锰的氧化物正极材料晶格中的可逆插入或脱出,同时以镍元素为主的负极材料进行氧化或镍离子(Ni2+)在负极表面还原的储能机理。由于其利用了镍离子(Ni2+)在锰的氧化物正极材料晶格中的可逆插入或脱出和镍离子(Ni2+)在负极表面的氧化或还原,并采用了特殊的电解质,因此,该电池具有可充电、循环寿命长、容量高等特点。
经实验证明,本发明电池的循环寿命可达1000次,远好于其它二次电池。同时这种可充电的镍离子电池还具有容量高、安全、环保、成本低廉等特点。可以预见这种镍离子电池可广泛应用于消费电子、电动车、通讯、航空航天和军事等领域。
附图说明
图1为实施例1制得的MnO2电极片在1mol L-1NiSO4电解液中扫描速率为1mV s-1时的单电极循环伏安图;
图2为实施例1制得的镍离子电池Cell 1在100mA g-1恒电流下第700次到710次循环的充放电曲线;
图3为实施例1制得的镍离子电池Cell 1的循环曲线;
图4为实施例2制得的镍离子电池Cell 2的恒电流充放电曲线;
图5为实施例3制得的镍离子电池Cell 3的恒电流充放电曲线。
具体实施方式
实施例1:
将MnO2(α-MnO2)粉末、导电剂碳黑和粘结剂聚偏四氟乙烯按质量比为7∶2∶1的比例混合后涂覆于不锈钢箔上,剪裁成一定大小,于真空中烘干为MnO2电极片。以该MnO2电极片为工作电极,以大面积活性炭电极为对电极,以Hg/Hg2SO4(in saturated K2SO4)为参比电极进行检测。该MnO2电极在1mol L-1NiSO4水溶液中的循环伏安图如图1,扫描速率为1mV s-1。从图中可以看出,当电位在一0.1V附近镍离子会嵌入MnO2晶格,而电位在0.2~0.6V vs.Hg/HgSO4之间镍离子可逆地脱出MnO2。
以制得的MnO2电极片为正极,以0.1mm厚的镍箔为负极,电解液为pH值为4.5的1mol L-1NiSO4水溶液组装成电池,记为Cell 1。Cell 1在100mA g-1(以正极活性物质质量计算)恒电流下第700次到710次循环的充放曲线如图2所示,由图2可见制得的Cell 1镍离子电池可重复充放电,为二次电池。以正极活性物质质量计算,Cell 1的容量为80mAh g-1。镍离子电池Cell 1的循环性能如图3所示,图中下方的为容量,上方的为库仑效率,可以看出,经过1000次循环,电池容量无衰减。
实施例2:
将Mn2O3、导电剂炭纳米管和粘结剂聚偏四氟乙烯按质量比为8∶0.5∶1.5的比例混合后涂覆于不锈钢箔上,剪裁成一定大小,于真空中烘干为Mn2O3电极片。以该制得的Mn2O3电极片为正极,以0.1mm厚的镍箔为负极,电解液为pH值为4.0的2mol L-1 NiSO4水溶液组装成可充电镍离子电池,记为Cell 2。Cell 2在100mA g-1(以正极活性物质质量计算)恒电流下充放电曲线如图4所示。以正极活性物质质量计算,电池Cell 2的容量为60mAh g-1。
实施例3:
镍粉电极制备过程如下:将镍粉、导电剂碳黑和粘结剂聚偏四氟乙烯按质量比为40∶50∶10的比例混合后,压于不锈钢箔上,剪裁成一定大小,于真空中烘干,制得镍粉电极。以实施例1制备的二氧化锰电极片为正极,以该制得的镍粉电极为负极,镍粉质量为二氧化锰质量的十倍,电解液为pH值为5.5的1mol L-1NiSO4水溶液组装成镍离子电池,记为Cell 3。Cell 3在100mA g-1(以正极活性物质质量计算)恒电流下充放电循环曲线见图5。以正极活性物质质量计算,电池Cell 3的容量为70mAh g-1。
Claims (9)
1.一种可充电的镍离子电池,由正极、负极、介于两者之间的隔离膜以及含有阴阳离子并具有离子导电性的电解质组成,其特征在于:
所述负极采用以镍元素为主的活性材料,
正极活性材料为可吸藏和释放镍离子的锰的氧化物材料,
所述电解质是以镍的可溶性盐为溶质,以水为溶剂,并具有离子导电性的液态或凝胶态材料,pH值介于3~7之间。
2.根据权利要求1所述的可充电的镍离子电池,其特征在于:构成正极活性材料的锰的氧化物材料为二氧化锰、三氧化二锰或四氧化三锰。
3.根据权利要求1所述的可充电的镍离子电池,其特征在于:所述负极是纯金属镍或镍的合金。
4.根据权利要求1所述的可充电的镍离子电池,其特征在于:所述负极包括集流体和集流体上的以镍粉末为主的活性材料,该活性材料是用镍粉和粘结剂制成的膜状材料。
5.根据权利要求4所述的可充电的镍离子电池,其特征在于:负极活性材料中还包括缓腐剂,缓腐剂的添加量为负极膜质量的1%以下。
6.根据权利要求5所述的可充电的镍离子电池,其特征在于:所述缓腐剂为铟的氧化物、或铟的氢氧化物。
7.根据权利要求5所述的可充电的镍离子电池,其特征在于:负极活性材料中还包括电子导电剂,电子导电剂的添加量为负极膜质量的50%以下。
8.根据权利要求4所述的可充电的镍离子电池,其特征在于:负极活性材料中还包括电子导电剂,电子导电剂的添加量为负极膜质量的50%以下。
9.根据权利要求1-8任一项所述的可充电的镍离子电池,其特征在于:所述镍的可溶性盐为硝酸镍、硫酸镍或氯化镍。
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