阅读说明：本技术 一种电化学脱锂制备高价过渡金属氧化物纳米材料的方法 (A kind of method that the de- lithium of electrochemistry prepares high valence transition metal oxide-based nanomaterial ) 是由 雷鸣 黄凯 许鹏富 张茹 于 2019-09-02 设计创作，主要内容包括：本发明涉及一种电化学脱锂制备高价过渡金属氧化物纳米材料的方法,属于材料科学与工程技术和化学领域。本发明方法制备的高价过渡金属氧化物材料包括由Fe、Co、Ni、Mn等过渡金属元素组成的纳米材料。通过制备出含锂过渡金属氧化物,在锂电池中进行电化学脱锂过程,从而使过渡金属价态升高,产生相应的脱锂高价过渡金属氧化物纳米材料。本发明具有制备工艺简单、速度快、效率高、应用范围广等优点。(The present invention relates to a kind of electrochemistry to take off the method that lithium prepares high valence transition metal oxide-based nanomaterial, belongs to Materials Science and Engineering technology and chemical field.The high valence transition metal oxide material of the method for the present invention preparation includes the nano material being made of transition metal elements such as Fe, Co, Ni, Mn.By preparing lithium-containing transition metal oxide, electrochemistry is carried out in lithium battery and takes off lithium process, so that transition metal valence state be made to increase, generate de- lithium high valence transition metal oxide-based nanomaterial accordingly.The present invention have many advantages, such as preparation process is simple, speed is fast, it is high-efficient, have a wide range of application.)

1. a kind of take off the method that lithium prepares high valence transition metal oxide-based nanomaterial using electrochemistry, it is characterised in that this method The following steps are included:

(1) it is mixed into fuse salt A with the lithium nitrate of 0.01-100mg and 0.01-100mg sodium nitrate, before 0.01-100mg is added It drives body to mix with fuse salt A, heating stirring 1-60min. waits for that reactant is cooled to room temperature at 200-600 DEG C, uses deionized water It rinses, finally the dry 12-24h in 20-100 DEG C of air environment, obtains lithium-containing transition metal oxide B.The forerunner Body is the monoatomic compound of transition metal, and the transition metal is monatomic for any one of Fe, Co, Ni, Mn.

(2) poly- with the conductive black of lithium-containing transition metal oxide B, 1-100% in above-mentioned (1) of 1-100% and 1-100% Vinylidene adhesive is raw material, prepares electrode slurries in a solvent.Then electrode slurries are coated on aluminium foil, dry 12- For 24 hours, anode C is obtained；Using lithium metal foil as battery cathode D；With the LiPF containing 0.01-6mol/L₆Ethylene carbonate and Carbonic acid divinyl (1:1) electrolyte is as electrolyte C.The anode C made and battery cathode D are then encased in pocket type electricity Electrolyte C is also added in bag-type battery, argon gas is finally passed through in bag-type battery by Chi Zhong.The solvent is water, second two Any one of alcohol, ethyl alcohol, tetraethylene-glycol, dimethylformamide or formaldehyde；

(3) battery is charged to high potential, carries out 1-100 charge/discharge cycle, positive product ethyl alcohol is rinsed into 1-10 It is secondary, after dry, obtain de- lithium high valence transition metal oxide-based nanomaterial.

(2) technical field

The present invention relates to electrochemistry to take off the method that lithium prepares high valence transition metal oxide-based nanomaterial, belongs to material science With engineering technology and chemical field.

(3) background technique

Currently, many approach have been proposed to realize that energy is more effectively converted or stored, fuel cell in scientists It is considered being most expected to become next-generation energy technology with metal-air cell technology.But the oxygen needed in their reaction process The activity of (OER) catalyst is precipitated in reduction (ORR) and oxygen and the not ideal enough business that restrict these technologies of stability uses. Most common effective oxygen reduction reaction catalyst is Pt, and oxygen evolution reaction catalyst is iridium dioxide (IrO₂) and titanium dioxide Ruthenium (RuO₂), but they are due to the use of noble metal so that catalyst holds at high price, so find it is a kind of efficiently and Cheap VPO catalysts are instantly most popular one of scientific research fields.

Transition metal oxide with extraordinary physically and electrically chemical property is considered as most possibly replacing due to it Noble metal, becoming one kind can be by the VPO catalysts of business promotion.There is good hydrogen reduction (ORR) and oxygen to be precipitated for they (OER) reactivity, and rich content, be easily obtained theoretical modeling and the experimental results showed that, transition metal oxide catalysis (OER) reactivity is precipitated in the hydrogen reduction (ORR) of agent and oxygen and the electronic structure of transition metal atoms is closely related, including oxygen Change state, e_gThe p of filling and O band center.Although find have new chemical component material be still one be worth research and very Interesting direction, but still an alternative is that develop a variety of different methods.We can the interior adjustment of extensive dynamic range again The electronic structure of current material, with optimizer catalytic activity.In the latest 20 years, electrochemistry of the lithium ion in organic bath is inserted Enter and extract and is widely used in rechargeable battery material.At the same time, the control of atomic ratio and electronic structure Tuning is also developed.We assume that such a continuous electronic structure adjustment oxide material is one big potential The chance that can improve catalyst activity is provided in range.In fact, some researches show that MoS₂Vertical layer nanometer film Electronic structure can take off insertion process of the lithium in organic bath by electrochemistry and be adjusted, thus after significantly improving Evolving hydrogen reaction (HER) activity in continuous aqueous solution again, its success motivate us to take off lithium using electrochemistry to tune hydrogen reduction (ORR) and (OER) process is precipitated in oxygen.

(4) summary of the invention

1, target of the invention

The purpose of the present invention is to propose to a kind of electrochemistry to take off the method that lithium prepares high valence transition metal oxide-based nanomaterial, Lithium-containing transition metal oxide catalytic performance is promoted, the method for lithium is taken off using electrochemistry, simply and effectively prepares a large amount of height The material of performance high valence transition metal oxide, and significantly reduce the cost of catalyst.

2, the invention main points of this technology

Main points of the present invention are as follows:

(1) LiNO of 0.01-100mg is used₃With the NaNO of 0.01-100mg₃It is mixed into fuse salt A, 0.01-100mg is added Presoma mixed with fuse salt A, heating stirring 1-60min. waits for that reactant is cooled to room temperature at 200-600 DEG C, spend from Sub- water rinses, and finally the dry 12-24h in 20-100 DEG C of air environment, obtains lithium-containing transition metal oxide B.Described Presoma is the monoatomic compound of transition metal, and the transition metal is monatomic for any one of Fe, Co, Ni, Mn.

(2) with the conductive black and 1- of lithium-containing transition metal oxide B, 1-100% in above-mentioned (1) of 1-100% 100% polyvinylidene fluoride binder is raw material, prepares electrode slurries in a solvent.Then electrode slurries are coated on aluminium foil, are done Dry 12-24h obtains anode C；Using lithium metal foil as battery cathode D；With the LiPF containing 0.01-6mol/L₆Carbonic acid second Alkene and carbonic acid divinyl (1:1) electrolyte are as electrolyte C.The anode C made and battery cathode D are then encased in bag In formula battery, electrolyte C is also added in bag-type battery, argon gas is finally passed through in bag-type battery.The solvent be water, Any one of ethylene glycol, ethyl alcohol, tetraethylene-glycol, dimethylformamide or formaldehyde；

(3) battery is charged to high potential, carries out 1-100 charge/discharge cycle, positive product ethyl alcohol is rinsed into 1- 10 times, after dry, obtain de- lithium high valence transition metal oxide-based nanomaterial.

Electrochemistry proposed by the present invention takes off the method that lithium prepares high valence transition metal oxide-based nanomaterial, its advantage is that: The method of the present invention can not only effectively control the de- lithium process of lithium-containing transition metal oxide, and available quick, efficient With high quality high valence transition metal oxide material applied widely, and preparation process is simply easy to operate.Energy of the present invention Various high valence transition metal oxide materials are enough prepared, such as the high price containing Fe, Co, Ni, Mn transition metal takes off the transition gold of lithium Belong to oxide.

(5) attached drawing of the invention

Fig. 1 is the scanning transmission electron microscope figure of the de- lithium high price Mn oxide of the method for the present invention preparation.

(6) embodiment of the present invention

The embodiment of the method for the present invention introduced below:

Embodiment 1

The preparation of de- lithium high price ferriferous oxide.

Firstly, the ferriferous oxide B containing lithium that synthesis needs, with the LiNO of 15mg₃With the NaNO of 18.5mg₃It is mixed into melting Salt A, with 4mg FeSO₄400 DEG C are heated to fuse salt A mixing, is rinsed, is obtained after dry containing lithium with deionized water later Ferriferous oxide B.Then with 80% the ferriferous oxide B containing lithium, 15% conductive black and 5% polyvinylidene fluoride binder The anode C made together with aluminium foil for the battery slurries that raw material makes in ultrapure water, the battery made with lithium metal foil Cathode D and LiPF containing 0.01mol/L₆Ethylene carbonate and carbonic acid divinyl (1:1) electrolyte fabrication electrolyte C production Then bag-type battery is passed through argon gas in bag-type battery.Last battery is incited somebody to action to 1 charge/discharge cycle of progress under high potential Anode is rinsed with ethyl alcohol, and de- lithium high price ferriferous oxide nano material is obtained after dry.