CN113120971B - 一种废旧三元正极材料的再生方法和应用 - Google Patents
一种废旧三元正极材料的再生方法和应用 Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 38
- 238000011069 regeneration method Methods 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 239000011572 manganese Substances 0.000 claims abstract description 24
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 2
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Abstract
本发明属于电池材料循环利用技术领域,公开了一种废旧三元正极材料的再生方法和应用,该再生方法包括以下步骤:取废旧三元正极材料进行烘干、破碎、筛分,得到正极粉;将正极粉加入碱液中反应,搅拌,洗涤,过滤得到滤渣;将滤渣进行烘干,再加入碳化沥青进行混合,进行还原煅烧,得到混合物;检测混合物中镍、钴、锰、铝、锂的含量,加入镍源、钴源、锂源、锰源,并加入聚乙二醇,球磨,加水,得到悬浊液将悬浊液进行喷雾造粒,得到三元前驱体;将三元前驱体进行两段烧结,即得再生的三元正极材料。本发明通过弱还原来实现废旧三元材料向氧化物的转变,从而解决物理法修复废旧电池的局限性。
Description
技术领域
本发明属于电池材料循环利用技术领域,具体涉及一种废旧三元正极材料的再生方法和应用。
背景技术
锂离子电池自20世纪末实现商业化以来,其以具有能量密度大、质量轻、寿命长且无记忆性等诸多优点,被广泛应用于动力、储能以及3C等领域,且动力和储能领域对锂电池的需求增速在不断加快。锂离子电池(LIBs)经过数百次循环充放电后,正负极材料会发生结构失效、SEI膜增厚、过渡金属溶出等不可逆的物理化学变化,进而阻碍Li+在正负极之间的嵌入/嵌脱反应,同时引起电池内阻急剧增加,最终造成LIBs的失活报废,所以锂离子电池的平均寿命只有2-3年。三元动力锂离子电池中含有大量的有价金属,通常Co约占5%-20%,Ni约占5%-12%,Mn约占7%-10%,Li约占2%-5%。如果可以将这些金属转化为可再利用资源,那么将创造巨大的经济效益。
目前,废旧锂离子电池正极再生回收方法主要有:沉淀分离法、共沉淀法、物理法修复再生。沉淀分离法和共沉淀法是指通过将废旧LiNixCoyMn1-x-yO2正极材料用无机酸或有机酸溶解,得到含有Li+、Ni2+、Co2+和Mn等离子的溶液,然后在其中加入相对应的沉淀剂,将上述离子选择性或者以同样速率沉淀成相对应的金属盐、(NixCoyMn1-x-y)CO3、NixCoyMn1-x-y(OH)2,金属盐可以重新作为制备前驱体的原料,而(NixCoyMn1-x-y)CO3、NixCoyMn1-x-y(OH)2可以直接补锂高温烧结得到三元正极材料。综上来说,沉淀分离法和共沉淀法回收产品纯度高,但工艺流程相对较为复杂,控制参数较多,同时会产生各种有危害的废液和气体,会造成二次污染。物理法修复再生很少用到无机酸或有机酸,产生废气和废水少,能够避免产生这些问题,可以很好地实现资源的无害化回收再生。其主要是对容量轻微衰减的三元材料直接进行混锂煅烧再生,首先通过水热补锂、熔融盐补锂,然后进行高温烧结原位逆向补锂修复再生。这种方法可以快速实现废旧锂离子电池正极材料循环再利用,但其对于废旧三元材料的电化学性能要求较高,如果废旧电池容量衰减比较严重(电极材料表面相变较多、金属溶出较多、微裂纹较多等),则会导致无法通过物理法来直接混锂煅烧再生。同时针对目前固相法再生、水热补锂再生、熔融盐补锂再生对废旧三元正极材料的品质要求较高,如果能够不用对废旧三元正极材料进行品质分级,直接进行回收再生,那么就能够节省大量的成本。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种废旧三元正极材料的再生方法和应用,该再生方法能简化品质分级流程、降低废液处理难度,实现巨大的经济利益;通过弱还原来实现废旧三元材料向氧化物的转变,从而解决物理法修复废旧电池的局限性。
为实现上述目的,本发明采用以下技术方案:
一种废旧三元正极材料的再生方法,包括以下步骤:
(1)取废旧三元正极材料进行烘干、破碎、筛分,得到正极粉;
(2)将所述正极粉加入碱液中反应,搅拌,洗涤,过滤得到滤渣;
(3)将所述滤渣进行烘干,再加入碳化沥青进行混合,进行还原煅烧,得到氧化镍、氧化锰、氧化钴、碳酸锂的混合物;
(4)检测所述混合物中镍、钴、锰、铝、锂的含量,加入镍源、钴源、锰源、锂源,并加入聚乙二醇,球磨,加水,得到悬浊液;
(5)将所述悬浊液进行喷雾造粒,得到三元前驱体;
(6)将所述三元前驱体进行两段烧结,即得再生的三元正极材料。
优选地,步骤(1)中,所述烘干的温度为150℃-200℃,时间为1-3h。
优选地,步骤(1)中,所述筛网的目数为200-300目。
优选地,步骤(2)中,所述反应的温度为60℃-90℃,反应的时间为10-60min。
优选地,步骤(2)中,所述碱液为氢氧化钠溶液,所述氢氧化钠溶液的温度为50℃-70℃,高温能够加快NaOH与正极粉中的铝反应,从而降低杂质铝的含量。
更优选地,所述氢氧化钠溶液的浓度为1-5mol/L。
优选地,步骤(3)中,所述正极粉与碳化沥青的质量比为1:(0.3-1.0);所述还原煅烧的温度为450℃-750℃,还原煅烧的时间为3-5h。
优选地,步骤(3)中,所述碳化沥青的处理工艺为在惰性气氛和1000℃-1300℃下将沥青进行煅烧1-3h,即得碳化沥青。
更优选地,所述惰性气氛为氮气、氦气、氩气中的一种。
优选地,步骤(4)中,所述聚乙二醇与正极粉的质量比为1:(0.1-0.30);所述混合物与水的质量体积比为(0.1-0.5):1g/mL。
优选地,步骤(4)中,按照摩尔比Ni:Co:Mn为6:2:2、1:1:1、5:2:3或8:1:1,添加镍源、锰源、钴源。
优选地,步骤(4)中,所述锂源为LiOH、乙酸锂或Li2CO3中的至少一种。
优选地,步骤(4)中,所述镍源为NiC4H6O4·4H2O或Ni(NO3)2·6H2O中的至少一种。
优选地,步骤(4)中,所述钴源为CoC4H6O4·4H2O或Co(NO3)2·6H2O中的至少一种。
优选地,步骤(4)中,所述锰源为MnC4H6O4·4H2O或Mn(NO3)2·6H2O中的至少一种。
优选地,步骤(4)中,所述球磨过程中使用的是超细球磨机;所述球磨的转速为600-1000r/min,球磨的时间为3-10h。
优选地,步骤(5)中,所述喷雾造粒的过程中使用的喷雾干燥机的喷雾温度为170-190℃,进料速度为300-650mL/h,进气压力为0.1-0.5MPa,出口温度为120-150℃。
优选地,步骤(6)中,所述两段烧结的具体步骤为:将所述三元前驱体进行第一段烧结,升温,再进行第二段烧结;所述第一段烧结的温度为400℃-500℃,第一段烧结的时间为5-8h;所述第二段的煅烧温度为700℃-900℃,第二段烧结的时间为10-20h。
步骤(3)的反应原理:
LiNixCoyMn1-x-yO2+沥青→xNiO+yMnO+(1-x-y)CoO+Li2CO3+H2O+CO2。
本发明还提供上述的再生方法在处理三元电池正极材料中的应用。
相对于现有技术,本发明的有益效果如下:
1.针对现有技术中物理法修复对废旧电池电化学性能要求较高的缺点,本发明主要通过弱还原来实现废旧三元材料向氧化物的转变,从而解决物理法修复废旧电池的局限性。其中碳化沥青具有弱的还原性,可以避免废旧三元材料转化为Ni、Co、Mn单质,从而转化为NiO、MnO、CoO、Li2CO3,然后重新原位合成出新正极材料,但是氧化物之间的固相反应面积较小,通过超细球磨可以使氧化物实现分子级的混合,从而使氧化物反应更充分,进而合成出性能较好的正极材料,此工艺无需复杂的控制条件,可以最大程度的实现元素的回收。
2.本发明再生的三元正极材料有一个较好的α-NaFeO2层状结构,没有杂相的存在,晶体结构良好。
3.本发明通过控制碳化沥青与废旧三元锂电池正极粉的比例、球磨参数,通过喷雾干燥可以实现不同系列三元材料产品生产的需求,方法操作简单、无污染、经济效益明显,为废旧锂电池三元正极材料回收再生提供了新的思路,具有巨大的工业应用前景。
附图说明
下面结合附图和实施例对本发明做进一步的说明,其中:
图1为本发明实施例1制备的NCM前驱体的SEM图;
图2为本发明实施例1制备再生的三元正极材料NCM523元素分布EDS图;
图3为本发明实施例1制备再生的三元正极材料NCM523的电化学性能图;
图4为本发明实施例2制备再生的三元正极材料NCM111的XRD图;
图5为还原球磨后与直接煅烧-球磨后再生三元材料电化学性能的对比图。
图6为本发明实施例3制备再生的三元正极材料NCM811的SEM图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
本实施例的废旧三元正极材料的再生方法,具体步骤如下:
(1)将电池容量衰减比较严重的废旧NCM523(LiNi0.5Co0.2Mn0.3O2)锂电池包置于3mol/L Na2SO4溶液中进行放电处理10h,并切割去除铝壳,分别得到电芯和外壳;
(2)将步骤(1)所得的电芯进行拆解得到正、负极片、隔膜、极耳,并将正极片进行200℃烘干1h;
(3)将步骤(2)所得的正极片进行破碎,过200目筛分,得到正极粉;
(4)将步骤(3)所得的正极粉放于3mol/L的NaOH溶液中,加热到75℃搅拌50min后除去电池粉中的铝,重复以上步骤三次以上,然后用去离子水清洗三次以上除去电池粉中的钠离子,过滤得到滤渣;
(5)将步骤(4)所得的滤渣放于干燥箱中进行100℃烘干10h,去除滤渣的水分;
(6)将步骤(5)所得的滤渣与碳化沥青(碳化工艺为将沥青在惰性气氛下1150℃煅烧2h)进行混合,滤渣与碳化沥青的质量比为1:0.7,并在惰性气氛下进行600℃煅烧4h,得到NiO、MnO、CoO、Li2CO3的混合物;
(7)检测步骤(6)获得的混合物的镍、钴、锰、锂的含量,按照比例添加NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O、C2H3O2Li,并加入聚乙二醇(聚乙二醇与废旧正极材料粉末质量比为0.2),混合物与水的质量体积比为0.3:1g/mL,然后在转速为750r/min的球磨机中进行球磨得到混合物,球磨的时间为7h,得到成分均一的悬浊液;
(8)将步骤(7)所得的悬浊液加到喷雾干燥机中,控制喷雾干燥机的温度为180℃,进料速度为450mL/h,进气压力0.5MPa,出口温度150℃,进行喷雾造粒,连续制备得到球型NCM523的前驱体;
(9)将步骤(8)制备出的NCM前驱体放于马弗炉中,加工业氧气进行两段煅烧,一段煅烧:升温至500℃,保温5h,再升温至850℃,保温15h进行二段煅烧,得到再生的三元正极材料NCM523。
图1为实施例1制备的NCM前驱体的SEM图,从图中可以看出前驱体呈类球状,直径分布在1-7μm。图2为实施例1制备的三元正极材料的EDS图,可以看出Ni、Co、Mn、O元素分布均匀,说明元素偏析较低,材料的均一性好。
实施例2
本实施例的废旧三元正极材料的再生方法,具体步骤如下:
(1)将电池容量衰减比较严重的废旧NCM111(LiNi0.3Co0.3Mn0.3O2)锂电池包置于3mol/L Na2SO4溶液中进行放电处理10h,并切割去除铝壳,分别得到电芯和外壳;
(2)将步骤(1)所得的电芯进行拆解得到正、负极片、隔膜、极耳,并将正极片进行150℃烘干3h;
(3)将步骤(2)所得的正极片进行破碎,过200目筛分,得到正极粉;
(4)将步骤(3)所得的正极粉放于1mol/L的NaOH溶液中,加热到90℃搅拌10min后除去电池粉中的铝,重复以上步骤三次以上,然后用去离子水清洗三次以上除去电池粉中的钠离子,过滤得到滤渣;
(5)将步骤(4)所得的滤渣放于干燥箱中进行100℃烘干10h,去除滤渣的水分;
(6)将步骤(5)所得的滤渣与碳化沥青(碳化工艺为将沥青在惰性气氛下1150℃煅烧2h)进行混合,滤渣与碳化沥青的质量比为1:0.7,并在惰性气氛下进行600℃煅烧4h,得到NiO、MnO、CoO、Li2CO3的混合物;
(7)检测步骤(6)获得的混合物的镍、钴、锰、锂的含量,按照比例添加NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O、C2H3O2L,并加入聚乙二醇(聚乙二醇与废旧正极材料粉末质量比为0.1),混合物与水的质量体积比g:mL为0.5:1,然后进行1000r/min的超细球磨得到混合物,球磨时间为3h,得到成分均一的悬浊液;
(8)将步骤(6)所得的悬浊液加到喷雾干燥机中,控制喷雾干燥机的温度为170℃,进料速度为650mL/h,进气压力0.1MPa,出口温度120℃,进行喷雾造粒,连续制备得到球型NCM111的前驱体;
(9)将步骤(8)制备出的NCM前驱体放于马弗炉中,加工业氧气进行两段煅烧,一段煅烧:升温至450℃,保温6h,再升温至900℃,保温12h进行二段煅烧,得到再生的三元正极材料NCM111。
实施例3
本实施例的废旧三元正极材料的再生方法,具体步骤如下:
(1)将废旧NCM811(LiNi0.8Co0.1Mn0.1O2)三元锂电池包置于3mol/L Na2SO4溶液中进行放电处理10h,并切割去除铝壳,分别得到电芯和外壳;
(2)将步骤(1)所得的电芯进行拆解得到正、负极片、隔膜、极耳,并将正极片进行170℃烘干2h;
(3)将步骤(2)所得的正极片进行破碎,过250目筛分,得到正极粉;
(4)将步骤(3)所得的正极粉放于5mol/L的NaOH溶液中,加热到60℃搅拌60min后除去电池粉中的铝,重复以上步骤三次以上,然后用去离子水清洗三次以上除去电池粉中的钠离子,过滤得到滤渣;
(5)将步骤(4)所得的滤渣放于干燥箱中进行100℃烘干10h,去除滤渣的水分;
(6)将步骤(5)所得的滤渣与碳化沥青(碳化工艺为将沥青在惰性气氛下1000℃煅烧3h)进行混合,滤渣与碳化沥青的质量比为1:1.0,并在惰性气氛下进行450℃煅烧5h,得到NiO、MnO、CoO、Li2CO3的混合物;
(7)检测步骤(6)获得的混合物的镍、钴、锰、锂的含量,按照比例添加NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O、C2H3O2Li,并加入聚乙二醇(聚乙二醇与废旧正极材料粉末质量比为0.3),混合物与水的质量体积比为0.1:1g/mL,然后进行600r/min的超细球磨得到混合物,球磨时间为10h,得到成分均一的悬浊液;
(8)将步骤(7)所得的悬浊液加到喷雾干燥机中,控制喷雾干燥机的温度为190℃,进料速度为450mL/h,进气压力0.3MPa,出口温度130℃,进行喷雾造粒,连续制备得到球型NCM811的前驱体;
(9)将步骤(8)制备出的NCM前驱体放于马弗炉中,加工业氧气进行两段煅烧,一段煅烧:升温至400℃,保温8h,再升温至700℃,保温20h进行二段煅烧,得到再生的三元正极材料NCM811。
图6为实施例3制备的三元正极材料的SEM图,从图中可以看出,再生制备的三元正极材料大部分颗粒为球形,二次颗粒由小的一次颗粒组成,且表面致密,有利于防止电解液对颗粒内部的腐蚀。
对比例1
对比例1为专利CN112186287A。
对比例2
本对比例的废旧三元正极材料的再生方法,具体步骤如下:
(1)将废旧NCM523(LiNi0.5Co0.2Mn0.3O2)三元锂电池包置于3mol/L Na2SO4溶液中进行放电处理10h,并切割去除铝壳,分别得到电芯和外壳;(2)将步骤(1)所得的电芯进行拆解得到正、负极片、隔膜、极耳,并将正极片进行200℃烘干1h;
(3)将步骤(2)所得的正极片进行破碎,过200目筛分,得到正极粉;
(4)将步骤(3)所得的正极粉放于3mol/L的NaOH溶液中,加热到75℃搅拌50min后除去电池粉中的铝,重复以上步骤三次以上,然后用去离子水清洗三次以上除去电池粉中的钠离子,过滤得到滤渣;
(5)将步骤(4)所得的滤渣放于干燥箱中进行100℃烘干10h,去除滤渣的水分;
(6)将步骤(5)所得的滤渣与弱还原剂(葡萄糖和柠檬酸)进行混合,滤渣与弱还原剂的质量比为1:0.7,并在惰性气氛下进行600℃煅烧4h,得到NiO、MnO、CoO、Li2CO3的混合物;
(7)检测步骤(6)获得的混合物的镍、钴、锰、锂的含量,按照比例添加NiC4H6O4·4H2O、CoC4H6O4·4H2O、MnC4H6O4·4H2O、C2H3O2Li,并加入聚乙二醇(聚乙二醇与废旧正极材料粉末质量比为0.2),混合物与水的质量体积比为0.3:1g/mL,然后在转速为750r/min的球磨机中进行球磨得到混合物,球磨的时间为7h,得到成分均一的悬浊液;
(8)将步骤(7)所得的悬浊液加到喷雾干燥机中,控制喷雾干燥机的温度为180℃,进料速度为450mL/h,进气压力0.5MPa,出口温度150℃,进行喷雾造粒,连续制备得到球型NCM523的前驱体;
(9)将步骤(8)制备出的NCM前驱体放于马弗炉中,加工业氧气进行两段煅烧,一段煅烧:升温至500℃,保温5h,再升温至850℃,保温15h进行二段煅烧,得到再生的三元正极材料NCM523。
对比对比例1,图3为本发明实施例1制备再生的三元正极材料NCM523的电化学性能图,从图3可以看出,本发明实施例1所选用的废旧电池,在1C下放电比容量只有100mAh/g左右,且衰减较快,说明废旧三元正极材料的电化学性能较差。而对比例1选用的废旧电池在1C下放电比容量为130mAh/g左右,循环性能较好。从再生三元正极材料的电化学性能来看,在0.1C首圈放电比容量为165.4mAh/g,1C首圈放电比容量为161.6mAh/g,循环充放电100圈后,容量保持率为94.8%,说明再生制备的正极材料具有良好的电化学性能。图4为实施例2制备的三元正极材料的XRD图,可以看出再生的三元正极材料有一个较好的α-NaFeO2层状结构,没有杂相的存在,晶体结构良好。
图5为还原球磨后与直接煅烧-球磨后再生三元材料电化学性能的对比图。从图5可以看出,直接煅烧-球磨后,在0.1C下其比容量仅为94.2mAh/g,1C下比容量仅为37.4mAh/g,200圈后比容量为19mAh/g,而还原球磨后其比容量发生了较大的变化,1C下首圈比容量为156.9mAh/g,200圈容量保持率为94.0%,说明了废旧电池电化学性能遭到了严重的不可逆损伤,无法直接通过物理法进行补锂,只有通过弱还原煅烧使三元材料转化为相应的氧化物,然后重新原位合成出新正极材料,说明本发明确实可以修复无法通过物理法修复的电池。
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (9)
1.一种废旧三元正极材料的再生方法,其特征在于,包括以下步骤:
(1)取废旧三元正极材料进行烘干、破碎、筛分,得到正极粉;
(2)将所述正极粉加入碱液中反应,搅拌,洗涤,过滤得到滤渣;
(3)将所述滤渣进行烘干,再加入碳化沥青进行混合,进行还原煅烧,得到氧化镍、氧化锰、氧化钴、碳酸锂的混合物;所述滤渣与所述碳化沥青的质量比为1:(0.7-1.0);
(4)检测所述混合物中镍、钴、锰、铝、锂的含量,加入镍源、钴源、锂源、锰源,并加入聚乙二醇,球磨,加水,得到悬浊液;
(5)将所述悬浊液进行喷雾造粒,得到三元前驱体;
(6)将所述三元前驱体进行两段烧结,即得再生的三元正极材料。
2.根据权利要求1所述的再生方法,其特征在于,步骤(1)中,所述烘干的温度为150℃-200℃,时间为1-3h。
3.根据权利要求1所述的再生方法,其特征在于,步骤(2)中,所述碱液为氢氧化钠溶液,所述氢氧化钠溶液的温度为50℃-70℃,浓度为1-5mol/L。
4.根据权利要求1所述的再生方法,其特征在于,步骤(4)中,所述锂源为LiOH、乙酸锂或Li2CO3中的至少一种。
5.根据权利要求1所述的再生方法,其特征在于,步骤(4)中,所述镍源为NiC4H6O4·4H2O或Ni(NO3)2·6H2O中的至少一种;步骤(4)中,所述钴源为CoC4H6O4·4H2O或Co(NO3)2·6H2O中的至少一种;步骤(4)中,所述锰源为MnC4H6O4·4H2O或Mn(NO3)2·6H2O中的至少一种。
6.根据权利要求1所述的再生方法,其特征在于,步骤(4)中,所述球磨过程中使用的是超细球磨机;所述球磨的转速为600-1000r/min,球磨的时间为3-10h。
7.根据权利要求1所述的再生方法,其特征在于,步骤(5)中,所述喷雾造粒的过程中使用的喷雾干燥机的喷雾温度为170℃-190℃,进料速度为300-650mL/h,进气压力为0.1-0.5MPa,出口温度为120℃-150℃。
8.根据权利要求1所述的再生方法,其特征在于,步骤(6)中,所述两段烧结的具体过程为:将所述三元前驱体进行第一段烧结,升温,再进行第二段烧结;所述第一段烧结的温度为400℃-500℃,第一段烧结的时间为5-8h;所述第二段的煅烧温度为700℃-900℃,第二段烧结的时间为10-20h。
9.权利要求1-8任一项所述的再生方法在处理三元电池正极材料中的应用。
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