纤维状多孔超细特种镍钴合金及复合氧化物粉末制备新方法研究
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摘要
特种超细粉末的许多特殊功能与它们的化学成分、组织结构以及粒度和形貌密切相关。而特种超细粉末的制备和加工方法是调变粉末特殊功能的一种必要手段，不仅可以不断创制出许多新材料而且也可以改变或精确控制许多传统粉体材料的成分、结构、形态和形貌等理化性能。因此研究制备特种超细粉体材料的新方法具有十分重要的实际应用价值和学术理论意义。
作者提出了在混合介质中(V_(溶剂A)∶V_(water)≥1∶3)采用配位共沉淀-热分解法制备纤维状多孔超细特种镍钴合金粉及其复合氧化物粉的新方法，并围绕其制备过程中粉末化学成分的均匀性、相组成和纯度、既定镍钴配比的维持、粉末粒度、形态和形貌控制等核心问题，系统地研究并成功解决了混合介质中配位共沉淀-热分解法制备过程中的一系列相关理论和实际应用过程中出现的难题。本论文主要论述了如下几个方面的研究内容：
发明了Ni~(2+)-Co~(2+)-NH_3-NH_4~+-C_2O_4~(2-)-H_2O-溶剂A体系中采用“配位共沉淀-热分解法”制备多孔特种镍钴合金粉末和镍钴复合氧化物粉末的新方法。新方法主要由配制镍钴均匀混合溶液、纤维状草酸镍钴复盐的合成、气氛调控下的热分解及特种镍钴合金粉末的表面防氧化处理等过程组成。全制备过程在常温常压下进行，易于实现产业化、对环境友好、可控性强，在同一个流程中只要改变热分解气氛即可获得两种完全不同的热分解产品。
通过理论和实验确定：在水介质中，当pH≤5.0时，可以得到维持设定镍钻配比的固溶体共沉淀物，然而当pH＞5.0时，草酸根离子与镍钴离子的共沉淀过程为分步沉淀，共沉淀物为混合物；在以溶剂A和水混合物的介质中，配位共沉淀法合成的镍钴合金或镍钴复合氧化物前驱体粉末，可以在一个很宽的pH值范围(2.0～8.6)内实现共沉淀产物中镍钴离子设定配比的精确控制和既定配比的稳定维持。采用热重／差热分析，X射线衍射分析和热磁分析证明了该pH值范围内得到的草酸镍钴复盐共沉淀产物均为单相共沉淀化合物，在弱还原性气氛中其热分解产物为镍钴合金粉末
首次在混合沉淀介质中配位共沉淀合成了粒状、棒状和纤维状形貌的草酸镍钴复盐粉末。系统考察了配位共沉淀过程中各工艺条件对共沉淀物粉末的成分、粒度及形貌的影响。结果表明：在制备纤维状草酸镍钴复盐粉末过程中，反应体系的温度，反应物浓度，溶液pH值，阴离子种类，分散剂，加料速度等因素均可影响共沉淀物的成分、形貌、粒度及分散性。以氨水作为配合剂和溶液pH值的调节剂，草酸或草酸铵为沉淀剂，反应温度为50～65℃，反加料方式，镍钴离子总浓度为0.5mol／L～0.8mol／L，阴离子为氯离子，分散剂为PVP，pH值为8.0～8.4条件下制得的草酸镍钴复盐粉末呈纤维状，轴径比大，镍钴离子配比准确，分散性好。同时固定其他条件，当pH≤5.0时，草酸镍钴复盐形貌为粒状聚集体；当pH=6.0～8.0时，草酸镍钴复盐形貌为棒状。
首次系统研究了不同条件下用配位共沉淀法合成的镍钴合金或镍钴复合氧化物前驱体粉末的形成机理和成分变化：用氨水调节溶液的pH值并当pH≤5.0时，前驱体粉末的分子式为Ni_xCo_(1-x)C_2O_4·2H_2O，其形貌呈粒状聚集体；而当pH=6.0～8.0或pH≥8.0时，由于部分氨参与共沉淀反应，前驱体分子式为Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O-nNH_3，其中x为摩尔分数，m、n和y为摩尔系数。m、n和y随反应pH值、氨浓度和干燥温度的不同而变化，变化范围为：y＜0.5，1.0＜m＜2.0，1.0＜n＜2.0；x值可通过控制原料中镍、钴离子的摩尔配比而得到精确控制，前驱体形貌分别呈棒状或纤维状。此外，还着重研究了形貌为棒状和纤维状的前驱体粉末(草酸镍钴复盐)的形成机理：草酸镍钴复盐分子晶体为一个二维平面结构的片状分子。在垂直于该片状分子的平面方向配合连接着L配位体，通过这些配体可构成沿轴向方向延伸生长的晶体粒子。当改变这些配位体时，草酸镍钴复盐晶体表面的极性得以改变，共沉淀产物即可通过轴向生长的[(NH_3)M-OX-M(NH_3)]~(2+)生长基元得以取向连生生长为棒状或纤维状草酸镍钴复盐粉末。
首次系统地研究了不同pH值条件下合成的不同形貌的草酸镍钴复盐粉末在氮气气氛中的热分解机理：
(a)pH≤5.0时，粒状草酸镍钴复盐粉末的热分解机理为：
Ni_xCo_(1-x)C_2O_4·2H_2O(?)Ni_xCo_(1-x)C_2O_4(?)Ni_xCo_(1-x)
(b)6.0≤pH＜8.8时，棒状和纤维状草酸镍钴复盐粉末的热分解机理为：
Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O·nNH_3(?)Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O(?)Ni_xCo_(1-x)(NH_3)_yC_2O_4(?)Ni_xCo_(1-x)C_2O_4(?)Ni_xCo_(1-x) solid solution
研究了草酸镍钴复盐粉末热分解条件对镍钴合金粉末理化性能的影响以及镍钴合金粉末表面防氧化的处理技术。热分解和表面处理两个过程在同一热分解炉内连续完成。研究结果表明：以配位共沉淀法合成的分散性好的纤维状草酸镍钴复盐粉末为原料，钝化剂C气体作为合金粉末防氧化处理钝化剂，在热分解温度为360℃～450℃，热分解时间为30分钟左右，热分解气氛为弱还原气氛，气流流速为1.2 L／min～1.8L／min以及随炉升温的条件下进行热分解反应即可得到疏松多孔、轴径比大、比表面积大、碳氧含量低、分散性好和不同配比的纤维状面心立方结构的镍钴合金粉末。
本项研究还发现，同样以纤维状草酸镍钴复盐粉末为原料，只要调控热分解温度和热分解气氛，还可制得纤维状多孔特种镍钴复合氧化物粉末。因而还首次系统研究了纤维状草酸镍钴复盐粉末在空气气氛中的热分解机理以及热分解条件对镍钴复合氧化物粉末物相的影响。结果表明：以Ni~(2+)／Co~(2+)=1：2的纤维状草酸镍钴复盐粉末为原料，在空气气氛中进行热分解，热分解温度为500℃左右，热分解时间为3小时条件下即可制得多孔的结构为Co_(1-x)~(2+)Co_x~(3+)[Co~(3+)Ni_y~(2+)Ni_(1-y)~(3+)]O_4的纤维状NiCo_2O_4复合氧化物粉末；热分解机理为首先脱去物理吸附水和代替部分结晶水的氨；随着温度的升高，然后失去结晶水，最后是脱配合氨、草酸镍钴热分解和镍钴氧化反应同时发生。
The distinctive properties of special ultrafine powders are closely related to their chemical compositions, structures and granularity as well as morphology. The preparation techniques and processing methods of ultrafine powders which are the necessary means for changing the product properties are able to not only create new materials, but also change and accurately control their physical and chemical properties such as chemical compositions, structures, granularity and morphology. Therefore, it is of great importance for practical application and fundamental academic study to explore novel preparation methods of ultrafine powders.A novel preparation method of coordination coprecipitation-pyrolytic decomposition was proposed to synthesize fibrous porous special ultrafine Ni-Co alloy and Ni-Co complex oxide powders in the mixed solvent of solvent A and water (V_(solvent A) :V_(water)≥1:3). The key properties of the two types of powders, including the uniformity of the chemical composition, phase composition, purity, specified ratios of Ni~(2+) to Co~(2+), and the control of granularity and morphology, were systematically investigated. The major research accomplishments in this paper are as follows:A novel method of coordination coprecipitation-pyrolytic decomposition in Ni~(2+)-Co~(2+)-NH_3-NH_4~+-C_2O_4~(2-)-H_2O-solvent A system was proposed to prepare fibrous porous special Ni-Co alloy and Ni-Co complex oxide powders. The process involves compounding uniformed mixture solution of nickel and cobalt ions, synthesis of fibrous nickel-cobalt oxalate complex salt, pyrolytic decomposition under the controlled atmospheric condition, and the surface oxidation resistance treatment of the powders. The process is carried out under ambient temperature and pressure. It is friendly to environment, easily operated and controlled, and therefore can be easily scaled up for commercial production. In addition, two different types of products can be obtained from the same process by adjusting pyrolytic decomposition atmosphere.The following conclusions were drawn from the theoretical analysis and experimental test. In the solvent of water, the coprecipitated solid solution with fixed ratio of Ni~(2+) to Co~(2+) can be obtained at pH＜5.0, as pH＞5.0, the precipitation process is fractiona and the precipitant is a mixture. In the mixed solvent of solvent A and water, when the precursor powders of Ni-Co solid solution alloy or Ni-Co complex oxide powders are synthesized by coordination coprecipitation, Ni~(2+) and Co~(2+) ratios can be controlled and maintained accurately within a wide range of pH values (2.0～8.6). For the first time, the coprecipitates synthesized in the mixed solvent with wide range of pH values (2.0～8.6) of solution have been validated as homogeneous Ni-Co oxalate complex salt compound by analytical methods of TGA/DTA and XRD. Similarly, the decomposition product obtained in weak reduce gas atmosphere with nitrogen and little hydrogen gas was confirmed by TGA/DTA, XRD as well as thermomagnetometry.
It is the first time to synthesize three different morphologies of Ni-Co oxalate complex salt including granular aggregation morphology, rod morphology and fibrous morphology by using coordination coprecipitation method in the mixed precipitating medium. The experimental conditions were investigated on the chemical composition, granularity and morphology of the coprecipitates. It can be concluded that the chemical composition, granularity and morphology of the coprecipitates are dependent on temperature, solution concentration, pH value, the nature of anions, dispersant, etc. The fibrous Ni-Co oxalate complex salt was obtained under the conditions of using ammonia as a complex and pH adjustor, oxalate as coprecipitated agent, reverse-feed method, temperature of 50～65℃, total concentration of Ni~(2+) and Co~(2+) of 0.5mol/L～0.8mol/L, PVP as dispersant, Cl~- as anion and pH value in the range of 8.0～8.4. The type of powders with rod morphology were obtained when pH is 6.0～8.0 and other conditions the same. The coprecipitate powders having granular aggregation morphology can be obtained when pH≤5.0.
For the first time, the mechanism of Ni-Co oxalate coprecipitation and differentce of the chemical compositions under different conditions were systematically studied. When pH≤5.0 by adjusting ammonia concentration, composition of the precursor is Ni_xCo_(1-x)C_2O_4·2H_2O and the morphology is granular aggregation; when pH=6.0～8.0 or pH≥8.0, the morphology of the precursor powders is rod-like or fibre-like respectively due to the involvement of ammonia in the coprecipitation process. The formula of the precursor were identified as Ni_xCo_(1-x) (NH_3)_yC_2O_4·mH_2O·nNH_3, where x represents molar fraction, while m, n and y represent mole numbers of the components which depend on the solution pH value, the concentration of ammonia and the drying temperature. The changing ranges of y, m, and n are as follows: 0＜y＜0.5, 1.0＜m＜2.0 and 1.0＜n＜2.0. The x value can be controlled accurately by manipulating the ratio of Ni~(2+) to Co~(2+) from the added feed metal salts. Additionally, the formation mechanism of fibrous or rod-like precursor powders (Ni-Co oxalate complex salt) was also investigated. For the Ni-Co oxalate complex salt, the central metal atom was bonded by two C_2O_4~(2-) ions forming a planar molecule. Perpendicular to the molecular plane are two coordinated H_2O molecules by which crystal grain can grow in an elongate way along axial direction. The surface polar of Ni-Co oxalate molecules is different when the complex switches from H_2O to NH_3 at different pH values in the solution by adding NH_3. Therefore, rod-like or fibre-like powders may be formed through [(NH_3)M-OX-M(NH_3)]~(2+) growth units along the axial direction.
For the first time, pyrolytic decomposition mechanism of Ni-Co oxalate complex salt obtained at different solution pH values with different morphologies were thoroughly explored in nitrogen atmosphere:
(a) When pH≤5.0, the decomposition mechanism of Ni-Co oxalate complex salt with granular aggregation morphology is described as follows:
Ni_xCo_(1-x)C_2O_4·2H_2O(?)Ni_xCo_(1-x)C_2O_4(?)Ni_xCo_(1-x) alloy
(b) when 6.0≤pH＜8.8, the decomposition mechanism of Ni-Co oxalate complex salt with rod-like or fibre-like morphology is described as follows:
Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O·nNH_3(?)Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O (?)Ni_xCo_(1-x)(NH_3)_yC_2O_4(?)Ni_xCo_(1-x)C_2O_4(?) Ni_xCo_(1-x) alloy
The effects of pyrolytic decomposition conditions of Ni-Co oxalate complex salt powders on the product performance and surface treatment were investigated. The pyrolytic decomposition process and surface treatment were conducted in the same furnace. The results showed that porous fibrous Ni-Co alloy powders with large aspect ratio, large specific surface area, low content of carbon and oxygen, well- dispensability and face-centered cubic structure can be obtained through the decomposition of Ni-Co oxalate complex salt under the condition of the proper decomposition: fibrous Ni-Co oxalate complex salt with good dispersion for precursor, weak reductive atmosphere, 360～450℃for decomposition temperature, 30 min for decomposition time, 1.2 L/min～1.8L/min for gas speed and heating up rates at 5～10℃/min.
It was also found that fibrous and porous special nickel-cobalt complex oxides powders can be produced by adjusting and controlling decomposition temperature and atmosphere if fibrous nickel-cobalt oxalate complex salt powders were taken as precursor of nickel-cobalt complex oxides. The pyrolytic decomposition mechanism of fibrous Ni-Co oxalate complex salt and the effects of pyrolytic decomposition conditions on the formation of Ni-Co complex oxides phase were systematically investigated for the first time. The results showed that porous fibrous NiCo_2O_4 complex oxide powders with Co_(1-x)~(2+)Co_x~(3+)[Co~(3+)Ni_y~(2+)Ni_(1-y)~(3+)]O_4 structure can be produced under the following conditions: fibrous Ni-Co oxalate complex salt powders with Ni~(2+)/Co~(2+)=1:2 (mole ratio) as decomposition material, flowing air or oxygen atmosphere, temperature 500℃and retention time 3 hours. Pyrolytic decomposition mechanism of Ni-Co oxalate complex salt in flowing air or oxygen atmosphere is as follow: First, physical absorbed water and ammonia substitution for hydrated water are deprived; and then dehydration process; last, deamination, decomposition of Ni_xCo_(1-x)CO_4 and oxidation of metal atom take place simultaneously.
作者提出了在混合介质中(V_(溶剂A)∶V_(water)≥1∶3)采用配位共沉淀-热分解法制备纤维状多孔超细特种镍钴合金粉及其复合氧化物粉的新方法，并围绕其制备过程中粉末化学成分的均匀性、相组成和纯度、既定镍钴配比的维持、粉末粒度、形态和形貌控制等核心问题，系统地研究并成功解决了混合介质中配位共沉淀-热分解法制备过程中的一系列相关理论和实际应用过程中出现的难题。本论文主要论述了如下几个方面的研究内容：
发明了Ni~(2+)-Co~(2+)-NH_3-NH_4~+-C_2O_4~(2-)-H_2O-溶剂A体系中采用“配位共沉淀-热分解法”制备多孔特种镍钴合金粉末和镍钴复合氧化物粉末的新方法。新方法主要由配制镍钴均匀混合溶液、纤维状草酸镍钴复盐的合成、气氛调控下的热分解及特种镍钴合金粉末的表面防氧化处理等过程组成。全制备过程在常温常压下进行，易于实现产业化、对环境友好、可控性强，在同一个流程中只要改变热分解气氛即可获得两种完全不同的热分解产品。
通过理论和实验确定：在水介质中，当pH≤5.0时，可以得到维持设定镍钻配比的固溶体共沉淀物，然而当pH＞5.0时，草酸根离子与镍钴离子的共沉淀过程为分步沉淀，共沉淀物为混合物；在以溶剂A和水混合物的介质中，配位共沉淀法合成的镍钴合金或镍钴复合氧化物前驱体粉末，可以在一个很宽的pH值范围(2.0～8.6)内实现共沉淀产物中镍钴离子设定配比的精确控制和既定配比的稳定维持。采用热重／差热分析，X射线衍射分析和热磁分析证明了该pH值范围内得到的草酸镍钴复盐共沉淀产物均为单相共沉淀化合物，在弱还原性气氛中其热分解产物为镍钴合金粉末
首次在混合沉淀介质中配位共沉淀合成了粒状、棒状和纤维状形貌的草酸镍钴复盐粉末。系统考察了配位共沉淀过程中各工艺条件对共沉淀物粉末的成分、粒度及形貌的影响。结果表明：在制备纤维状草酸镍钴复盐粉末过程中，反应体系的温度，反应物浓度，溶液pH值，阴离子种类，分散剂，加料速度等因素均可影响共沉淀物的成分、形貌、粒度及分散性。以氨水作为配合剂和溶液pH值的调节剂，草酸或草酸铵为沉淀剂，反应温度为50～65℃，反加料方式，镍钴离子总浓度为0.5mol／L～0.8mol／L，阴离子为氯离子，分散剂为PVP，pH值为8.0～8.4条件下制得的草酸镍钴复盐粉末呈纤维状，轴径比大，镍钴离子配比准确，分散性好。同时固定其他条件，当pH≤5.0时，草酸镍钴复盐形貌为粒状聚集体；当pH=6.0～8.0时，草酸镍钴复盐形貌为棒状。
首次系统研究了不同条件下用配位共沉淀法合成的镍钴合金或镍钴复合氧化物前驱体粉末的形成机理和成分变化：用氨水调节溶液的pH值并当pH≤5.0时，前驱体粉末的分子式为Ni_xCo_(1-x)C_2O_4·2H_2O，其形貌呈粒状聚集体；而当pH=6.0～8.0或pH≥8.0时，由于部分氨参与共沉淀反应，前驱体分子式为Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O-nNH_3，其中x为摩尔分数，m、n和y为摩尔系数。m、n和y随反应pH值、氨浓度和干燥温度的不同而变化，变化范围为：y＜0.5，1.0＜m＜2.0，1.0＜n＜2.0；x值可通过控制原料中镍、钴离子的摩尔配比而得到精确控制，前驱体形貌分别呈棒状或纤维状。此外，还着重研究了形貌为棒状和纤维状的前驱体粉末(草酸镍钴复盐)的形成机理：草酸镍钴复盐分子晶体为一个二维平面结构的片状分子。在垂直于该片状分子的平面方向配合连接着L配位体，通过这些配体可构成沿轴向方向延伸生长的晶体粒子。当改变这些配位体时，草酸镍钴复盐晶体表面的极性得以改变，共沉淀产物即可通过轴向生长的[(NH_3)M-OX-M(NH_3)]~(2+)生长基元得以取向连生生长为棒状或纤维状草酸镍钴复盐粉末。
首次系统地研究了不同pH值条件下合成的不同形貌的草酸镍钴复盐粉末在氮气气氛中的热分解机理：
(a)pH≤5.0时，粒状草酸镍钴复盐粉末的热分解机理为：
Ni_xCo_(1-x)C_2O_4·2H_2O(?)Ni_xCo_(1-x)C_2O_4(?)Ni_xCo_(1-x)
(b)6.0≤pH＜8.8时，棒状和纤维状草酸镍钴复盐粉末的热分解机理为：
Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O·nNH_3(?)Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O(?)Ni_xCo_(1-x)(NH_3)_yC_2O_4(?)Ni_xCo_(1-x)C_2O_4(?)Ni_xCo_(1-x) solid solution
研究了草酸镍钴复盐粉末热分解条件对镍钴合金粉末理化性能的影响以及镍钴合金粉末表面防氧化的处理技术。热分解和表面处理两个过程在同一热分解炉内连续完成。研究结果表明：以配位共沉淀法合成的分散性好的纤维状草酸镍钴复盐粉末为原料，钝化剂C气体作为合金粉末防氧化处理钝化剂，在热分解温度为360℃～450℃，热分解时间为30分钟左右，热分解气氛为弱还原气氛，气流流速为1.2 L／min～1.8L／min以及随炉升温的条件下进行热分解反应即可得到疏松多孔、轴径比大、比表面积大、碳氧含量低、分散性好和不同配比的纤维状面心立方结构的镍钴合金粉末。
本项研究还发现，同样以纤维状草酸镍钴复盐粉末为原料，只要调控热分解温度和热分解气氛，还可制得纤维状多孔特种镍钴复合氧化物粉末。因而还首次系统研究了纤维状草酸镍钴复盐粉末在空气气氛中的热分解机理以及热分解条件对镍钴复合氧化物粉末物相的影响。结果表明：以Ni~(2+)／Co~(2+)=1：2的纤维状草酸镍钴复盐粉末为原料，在空气气氛中进行热分解，热分解温度为500℃左右，热分解时间为3小时条件下即可制得多孔的结构为Co_(1-x)~(2+)Co_x~(3+)[Co~(3+)Ni_y~(2+)Ni_(1-y)~(3+)]O_4的纤维状NiCo_2O_4复合氧化物粉末；热分解机理为首先脱去物理吸附水和代替部分结晶水的氨；随着温度的升高，然后失去结晶水，最后是脱配合氨、草酸镍钴热分解和镍钴氧化反应同时发生。
The distinctive properties of special ultrafine powders are closely related to their chemical compositions, structures and granularity as well as morphology. The preparation techniques and processing methods of ultrafine powders which are the necessary means for changing the product properties are able to not only create new materials, but also change and accurately control their physical and chemical properties such as chemical compositions, structures, granularity and morphology. Therefore, it is of great importance for practical application and fundamental academic study to explore novel preparation methods of ultrafine powders.A novel preparation method of coordination coprecipitation-pyrolytic decomposition was proposed to synthesize fibrous porous special ultrafine Ni-Co alloy and Ni-Co complex oxide powders in the mixed solvent of solvent A and water (V_(solvent A) :V_(water)≥1:3). The key properties of the two types of powders, including the uniformity of the chemical composition, phase composition, purity, specified ratios of Ni~(2+) to Co~(2+), and the control of granularity and morphology, were systematically investigated. The major research accomplishments in this paper are as follows:A novel method of coordination coprecipitation-pyrolytic decomposition in Ni~(2+)-Co~(2+)-NH_3-NH_4~+-C_2O_4~(2-)-H_2O-solvent A system was proposed to prepare fibrous porous special Ni-Co alloy and Ni-Co complex oxide powders. The process involves compounding uniformed mixture solution of nickel and cobalt ions, synthesis of fibrous nickel-cobalt oxalate complex salt, pyrolytic decomposition under the controlled atmospheric condition, and the surface oxidation resistance treatment of the powders. The process is carried out under ambient temperature and pressure. It is friendly to environment, easily operated and controlled, and therefore can be easily scaled up for commercial production. In addition, two different types of products can be obtained from the same process by adjusting pyrolytic decomposition atmosphere.The following conclusions were drawn from the theoretical analysis and experimental test. In the solvent of water, the coprecipitated solid solution with fixed ratio of Ni~(2+) to Co~(2+) can be obtained at pH＜5.0, as pH＞5.0, the precipitation process is fractiona and the precipitant is a mixture. In the mixed solvent of solvent A and water, when the precursor powders of Ni-Co solid solution alloy or Ni-Co complex oxide powders are synthesized by coordination coprecipitation, Ni~(2+) and Co~(2+) ratios can be controlled and maintained accurately within a wide range of pH values (2.0～8.6). For the first time, the coprecipitates synthesized in the mixed solvent with wide range of pH values (2.0～8.6) of solution have been validated as homogeneous Ni-Co oxalate complex salt compound by analytical methods of TGA/DTA and XRD. Similarly, the decomposition product obtained in weak reduce gas atmosphere with nitrogen and little hydrogen gas was confirmed by TGA/DTA, XRD as well as thermomagnetometry.
It is the first time to synthesize three different morphologies of Ni-Co oxalate complex salt including granular aggregation morphology, rod morphology and fibrous morphology by using coordination coprecipitation method in the mixed precipitating medium. The experimental conditions were investigated on the chemical composition, granularity and morphology of the coprecipitates. It can be concluded that the chemical composition, granularity and morphology of the coprecipitates are dependent on temperature, solution concentration, pH value, the nature of anions, dispersant, etc. The fibrous Ni-Co oxalate complex salt was obtained under the conditions of using ammonia as a complex and pH adjustor, oxalate as coprecipitated agent, reverse-feed method, temperature of 50～65℃, total concentration of Ni~(2+) and Co~(2+) of 0.5mol/L～0.8mol/L, PVP as dispersant, Cl~- as anion and pH value in the range of 8.0～8.4. The type of powders with rod morphology were obtained when pH is 6.0～8.0 and other conditions the same. The coprecipitate powders having granular aggregation morphology can be obtained when pH≤5.0.
For the first time, the mechanism of Ni-Co oxalate coprecipitation and differentce of the chemical compositions under different conditions were systematically studied. When pH≤5.0 by adjusting ammonia concentration, composition of the precursor is Ni_xCo_(1-x)C_2O_4·2H_2O and the morphology is granular aggregation; when pH=6.0～8.0 or pH≥8.0, the morphology of the precursor powders is rod-like or fibre-like respectively due to the involvement of ammonia in the coprecipitation process. The formula of the precursor were identified as Ni_xCo_(1-x) (NH_3)_yC_2O_4·mH_2O·nNH_3, where x represents molar fraction, while m, n and y represent mole numbers of the components which depend on the solution pH value, the concentration of ammonia and the drying temperature. The changing ranges of y, m, and n are as follows: 0＜y＜0.5, 1.0＜m＜2.0 and 1.0＜n＜2.0. The x value can be controlled accurately by manipulating the ratio of Ni~(2+) to Co~(2+) from the added feed metal salts. Additionally, the formation mechanism of fibrous or rod-like precursor powders (Ni-Co oxalate complex salt) was also investigated. For the Ni-Co oxalate complex salt, the central metal atom was bonded by two C_2O_4~(2-) ions forming a planar molecule. Perpendicular to the molecular plane are two coordinated H_2O molecules by which crystal grain can grow in an elongate way along axial direction. The surface polar of Ni-Co oxalate molecules is different when the complex switches from H_2O to NH_3 at different pH values in the solution by adding NH_3. Therefore, rod-like or fibre-like powders may be formed through [(NH_3)M-OX-M(NH_3)]~(2+) growth units along the axial direction.
For the first time, pyrolytic decomposition mechanism of Ni-Co oxalate complex salt obtained at different solution pH values with different morphologies were thoroughly explored in nitrogen atmosphere:
(a) When pH≤5.0, the decomposition mechanism of Ni-Co oxalate complex salt with granular aggregation morphology is described as follows:
Ni_xCo_(1-x)C_2O_4·2H_2O(?)Ni_xCo_(1-x)C_2O_4(?)Ni_xCo_(1-x) alloy
(b) when 6.0≤pH＜8.8, the decomposition mechanism of Ni-Co oxalate complex salt with rod-like or fibre-like morphology is described as follows:
Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O·nNH_3(?)Ni_xCo_(1-x)(NH_3)_yC_2O_4·mH_2O (?)Ni_xCo_(1-x)(NH_3)_yC_2O_4(?)Ni_xCo_(1-x)C_2O_4(?) Ni_xCo_(1-x) alloy
The effects of pyrolytic decomposition conditions of Ni-Co oxalate complex salt powders on the product performance and surface treatment were investigated. The pyrolytic decomposition process and surface treatment were conducted in the same furnace. The results showed that porous fibrous Ni-Co alloy powders with large aspect ratio, large specific surface area, low content of carbon and oxygen, well- dispensability and face-centered cubic structure can be obtained through the decomposition of Ni-Co oxalate complex salt under the condition of the proper decomposition: fibrous Ni-Co oxalate complex salt with good dispersion for precursor, weak reductive atmosphere, 360～450℃for decomposition temperature, 30 min for decomposition time, 1.2 L/min～1.8L/min for gas speed and heating up rates at 5～10℃/min.
It was also found that fibrous and porous special nickel-cobalt complex oxides powders can be produced by adjusting and controlling decomposition temperature and atmosphere if fibrous nickel-cobalt oxalate complex salt powders were taken as precursor of nickel-cobalt complex oxides. The pyrolytic decomposition mechanism of fibrous Ni-Co oxalate complex salt and the effects of pyrolytic decomposition conditions on the formation of Ni-Co complex oxides phase were systematically investigated for the first time. The results showed that porous fibrous NiCo_2O_4 complex oxide powders with Co_(1-x)~(2+)Co_x~(3+)[Co~(3+)Ni_y~(2+)Ni_(1-y)~(3+)]O_4 structure can be produced under the following conditions: fibrous Ni-Co oxalate complex salt powders with Ni~(2+)/Co~(2+)=1:2 (mole ratio) as decomposition material, flowing air or oxygen atmosphere, temperature 500℃and retention time 3 hours. Pyrolytic decomposition mechanism of Ni-Co oxalate complex salt in flowing air or oxygen atmosphere is as follow: First, physical absorbed water and ammonia substitution for hydrated water are deprived; and then dehydration process; last, deamination, decomposition of Ni_xCo_(1-x)CO_4 and oxidation of metal atom take place simultaneously.
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