阅读说明：本技术 钛酸锂材料的制备方法 (The preparation method of lithium titanate material ) 是由 申大卫 陈夏成 于 2019-08-26 设计创作，主要内容包括：本发明涉及一种钛酸锂材料的制备方法,属于电极材料技术领域。钛酸锂材料的制备方法包含有如下步骤：①将钛源、易溶锂源与浆料介质相混合制得浆料；②将所述浆料进行干燥,得到干燥料；③将所述干燥料进行烧制,得到烧制料；④将所述烧制料进行粉碎,得到钛酸锂材料。该制备方法使物相接触更均匀、反应更完全,制得的钛酸锂容量更接近理论值,可逆性能(循环性能)更好,一致性更高,相对应的储能器件寿命就更长；且制备过程中用水量更少,对环境更友好。(The present invention relates to a kind of preparation methods of lithium titanate material, belong to electrode material technical field.The preparation method of lithium titanate material includes to have the following steps: titanium source, readily soluble lithium source and slurry medium 1. being mixed obtained slurry；2. the slurry is dried, dried feed is obtained；3. the dried feed is fired, obtain firing material；4. firing material is crushed, lithium titanate material is obtained.The preparation method make object be in contact more evenly, reaction it is more complete, lithium titanate capacity obtained is closer to theoretical value, and more preferably, consistency is higher for reversibility (cycle performance), and the corresponding energy storage device service life is with regard to longer；And water consumption is less in preparation process, to more environment-friendly.)

1. the preparation method of lithium titanate material, which is characterized in that comprising having the following steps:

1. prepared by slurry: titanium source, readily soluble lithium source and slurry medium being mixed obtained slurry, wherein the readily soluble lithium source is at least It include the compound of lithium of the solubility greater than 10g/100ml in 20 DEG C of water, the slurry medium, which includes at least, water；

2. drying: the slurry being dried, dried feed is obtained；

3. firing: the dried feed being fired, obtains firing material；

4. crushing: firing material being crushed, lithium titanate material is obtained.

2. the preparation method of lithium titanate material according to claim 1, it is characterised in that: the compound of the lithium is by carbonic acid Lithium or Lithium hydroxide monohydrate or lithium hydroxide react generation with acid.

3. the preparation method of lithium titanate material according to claim 2, it is characterised in that: the acid be formic acid, acetic acid, Propionic acid, butyric acid, valeric acid, acid, isobutyric acid, lactic acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedioic acid, apple One of acid, tartaric acid, butene dioic acid, polyacrylic acid or a variety of mixtures.

4. the preparation method of lithium titanate material according to claim 1, it is characterised in that: the compound of the lithium is formic acid Lithium, propionic acid lithium, n-butyric acie lithium, isobutyric acid lithium, lithium valerate, sour lithium, lithium lactate, lithium citrate, hydrogen citrate lithium, oxalic acid hydrogen Lithium, Lithium malonate, malonic acid hydrogen lithium, succinic acid lithium, succinic acid hydrogen lithium, glutaric acid lithium, glutaric acid hydrogen lithium, hexanedioic acid lithium, two Sour hydrogen lithium, butenoic acid lithium, butenoic acid hydrogen lithium, malic acid lithium, hydrogen malate lithium, lithium tartrate, lithium bitartrate, polyacrylic acid One of lithium, polyacrylic acid hydrogen lithium or a variety of compositions.

5. the preparation method of lithium titanate material according to claim 1, it is characterised in that: step 1. in, the titanium source is Titanium dioxide or metatitanic acid.

6. the preparation method of lithium titanate material according to claim 1, it is characterised in that: step 1. in, the slurry is situated between Matter is water, and the mass ratio that water accounts for the slurry is 20% ~ 80%.

7. the preparation method of lithium titanate material according to claim 1, it is characterised in that: step 1. in, in the slurry, It also include the modified material for modified lithium titanate material.

8. the preparation method of lithium titanate material according to claim 1, it is characterised in that: step 1. in, hybrid mode choosing With one of ball milling, sand milling, mechanical stirring dispersion, ultrasonic wave dispersion or a variety of combinations.

9. the preparation method of lithium titanate material according to claim 1, it is characterised in that: step 2. in, to the slurry It is spray-dried or is dried drying.

10. the preparation method of lithium titanate material according to claim 1, it is characterised in that: step 3. in, to the drying The firing temperature section of material is 700 DEG C ~ 900 DEG C, and the firing time is 3 ~ 12 hours.

11. the preparation method of lithium titanate material according to claim 1, it is characterised in that: step 4. in, to the firing Material carries out mechanical crushing or air-flow crushing.

Technical field

The present invention relates to electrode material technical fields, and in particular to a kind of preparation method of lithium titanate material.

Background technique

With the development of social economy and the sternness of Environmental Protection Situation, requirement of the market to energy storage device is higher and higher, and stores up Energy material is in core status again in energy storage device.Lithium titanate is as one of energy storage field important materials, because it has Security performance is high, operating temperature is wide, high rate performance is excellent, the advantages that having extended cycle life, particularly suitable for high power, long-time, low The application scenarios such as temperature/high temperature, high safety.

Wherein security performance, high rate performance are largely to be restricted by material intrinsic property, but cycle performance removes Restricted by the intrinsic property of material outer, the component part and process conditions of energy storage device equally play highly important shadow to it It rings.

Lithium titanate is the uniformly mixed journey of titanium source and lithium source as a kind of important energy storage material, one of key of preparation Degree.Titanium source and lithium source mix more uniform, and the sintering procedure in later period is easier, the lithium titanate capacity of firing closer to theoretical value, Cycle performance is better, and consistency is higher, and the energy storage device service life that such material is made into is longer.Industrial production lithium titanate at present Titanium source be mainly titanium dioxide and metatitanic acid, the two is all insoluble solid matter；There are mainly two types of lithium sources in the market, carbon Sour lithium and lithium hydroxide (or an anhydrous water lithium hydroxide), such as the Chinese invention patent that application publication number is 108622930 A of CN A kind of preparation method of lithium titanate material is disclosed, uses at least one of titanium dioxide and meta-acid titanium for titanium source, is used One of Lithium hydroxide monohydrate, lithium carbonate prepare lithium titanate material as lithium source.When using lithium carbonate as lithium source, firing Lithium titanate capacity differs farther out with its theoretical value；And oxygen lithium hydride is that lithium source material prepares lithium titanate, it as a result will be much better, still For lithium hydroxide during preparing lithium titanate, there are three problems: 1. solubility is still not big enough, leads to be added a large amount of water It can be uniformly mixed；2. alkaline strong, big to personnel, equipment damage, environment is not friendly enough；3. price is with respect to lithium carbonate height.

Summary of the invention

In view of the above-mentioned problems, the present invention provides a kind of preparation method of lithium titanate material, object is made to be in contact more evenly, reaction More completely；For lithium titanate capacity closer to theoretical value, cycle performance is more preferable, and consistency is higher, and the corresponding energy storage device service life is just It is longer；And energy consumption is lower in preparation process, water consumption is less, to more environment-friendly.

Technical scheme is as follows:

The preparation method of lithium titanate material, comprising having the following steps:

1. prepared by slurry: titanium source, readily soluble lithium source and slurry medium being mixed obtained slurry, wherein the readily soluble lithium source is at least It include the compound of lithium of the solubility greater than 10g/100ml in 20 DEG C of water, the slurry medium, which includes at least, water；

Typically, the effective component in titanium source is the mixture of one or both of titanium dioxide, metatitanic acid, titanium in titanium source The ratio between amount of substance of lithium atom is 4 ~ 5:5 in the amount of the substance of atom and readily soluble lithium source；

2. drying: the slurry being dried, dried feed is obtained；

3. firing: the dried feed being fired, obtains firing material；

4. crushing: firing material being crushed, lithium titanate material is obtained.

As a preferred embodiment of the above technical solution, the compound of the lithium is by lithium carbonate or Lithium hydroxide monohydrate or anhydrous hydrogen-oxygen Change lithium and reacts generation with acid.

Particularly, the acid reacted with lithium carbonate or Lithium hydroxide monohydrate or lithium hydroxide is including but not limited to below Acid: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, lactic acid, citric acid, oxalic acid, malonic acid, succinic acid, penta 2 Acid, adipic acid, malic acid, tartaric acid, butene dioic acid, polyacrylic acid.Lithium carbonate or Lithium hydroxide monohydrate (or anhydrous hydroxide Lithium) when reacting with binary or polyacid, by adjusting the ratio of reactant, normal salt and acid salt can be respectively obtained；It can also be with With two or more sour simultaneous reactions, mixing hydrochlorate is obtained.

Present inventor by common lithium source material lithium carbonate or Lithium hydroxide monohydrate (or lithium hydroxide) with have Machine acid is reacted, and common lithium source is optimized for organic acid lithium salts, this easy reaction will be existing with lower cost Indissoluble lithium source (lithium carbonate) or strong basicity lithium source (Lithium hydroxide monohydrate or lithium hydroxide) be changed to readily soluble and faintly acid, neutrality Or weakly alkaline organic acid lithium salts.

As a preferred embodiment of the above technical solution, the compound of the lithium is lithium formate, propionic acid lithium, n-butyric acie lithium, isobutyric acid Lithium, lithium valerate, caproic acid lithium, glutaric acid lithium, glutaric acid hydrogen lithium, lithium adipate, adipic acid hydrogen lithium, lithium lactate, lithium citrate, lemon Sour hydrogen lithium, malic acid lithium, hydrogen malate lithium, lithium tartrate, lithium bitartrate, oxalic acid hydrogen lithium, Lithium malonate, malonic acid hydrogen lithium, One of succinic acid lithium, succinic acid hydrogen lithium, butene dioic acid lithium, butene dioic acid hydrogen lithium, Lithium polyacrylate, polyacrylic acid hydrogen lithium or A variety of compositions.

Lithium carbonate is insoluble in water, so if preparing lithium titanate using metatitanic acid or titanium dioxide and lithium carbonate as raw material, it is difficult To realize the uniform mixing of titanium, elemental lithium, cause the reaction of sintering procedure close to solid phase and solid phase reaction be difficult to realize uniformly, Complete reaction.

Lithium hydroxide basic is strong, big to personnel, equipment damage, not friendly enough to environment, and its price is inclined with respect to lithium carbonate It is high.

The readily soluble lithium source used in the present invention abundant, homogeneous can be scattered in slurry medium, i.e., titanium easy to accomplish, lithium The uniform mixing of element；And the fusing point of these readily soluble organic acid lithium salts is lower, so that the reaction of sintering procedure is close to liquid phase Reacting between solid phase, so that reaction is more evenly, completely, the lithium titanate capacity so prepared is closer to theoretical value.

Meanwhile inventor has found: using organic acid lithium as lithium source, the lithium titanate crystal form of prepared lithium titanate material is more Regular neat, primary particle is smaller, thus also brings the promotion of lithium titanate material performance.

And the organic acid lithium salts of above-mentioned lithium is close to faintly acid, neutrality or alkalescent, the damage to operator and equipment compared with It is small, it is environmentally friendly.

From other technical concept, also has use the organic lithium salts such as lithium formate, lithium acetate, propionic acid lithium in the prior art Make chelating agent with enhance lithium titanate material it is compound, improve correlated performance, organic lithium salt role and its in this Shen Please played in effect it is not identical.

As a preferred embodiment of the above technical solution, the titanium source is titanium dioxide or metatitanic acid.

As a preferred embodiment of the above technical solution, step 1. in, the slurry medium is water, and water accounts for the quality hundred of the slurry Divide than being 20% ~ 80%；The effect that water primarily serves dissolution lithium source, disperses titanium source.

As a preferred embodiment of the above technical solution, step 1. in, also include for being modified in the slurry medium in addition to water The modified material of lithium titanate material；Modified material includes: boric acid, boron oxide, lithium borate, niobium oxide, zirconium oxide etc., is mainly mentioned The capacity and cycle life of high lithium titanate material.

As a preferred embodiment of the above technical solution, step 1. in, hybrid mode selects ball milling, sand milling, mechanical stirring dispersion, super One of sound wave dispersion or a variety of combinations.

As a preferred embodiment of the above technical solution, step 2. in, the slurry is spray-dried or is dried drying.

As a preferred embodiment of the above technical solution, step 3. in, be 700 DEG C ~ 900 to the firing temperature section of the dried feed DEG C, the firing time is 3 ~ 12 hours.

As a preferred embodiment of the above technical solution, step 4. in, to the firing material carry out be mechanically pulverized or air-flow crushing.

In conclusion the invention has the following advantages:

The present invention provides a kind of preparation method of lithium titanate material, has the following beneficial effects:

1. making the reaction in firing stage, lithium titanate capacity is closer to theoretical value (175mAh/g), and cycle performance is more more evenly, completely Good, consistency is higher, and the corresponding energy storage device service life is with regard to longer；

2. water consumption is less in preparation process, energy consumption is lower；

3. strong alkaline substance is not used in preparation process, it is smaller, lower to equipment damage to operator's injury, it is more friendly to environment It is good.

Detailed description of the invention

Fig. 1 is the electromicroscopic photograph of lithium titanate material made from comparative example 1；

Fig. 2 is the electromicroscopic photograph of lithium titanate material made from embodiment 1；

Fig. 3 is the electromicroscopic photograph of lithium titanate material made from embodiment 2；

Fig. 4 is the charging and discharging curve figure of lithium titanate material made from comparative example 1；

Fig. 5 is the charging and discharging curve figure of lithium titanate material made from comparative example 2；

Fig. 6 is the charging and discharging curve figure of lithium titanate material made from embodiment 1；

Fig. 7 is the charging and discharging curve figure of lithium titanate material made from embodiment 2；

Fig. 8 is the charging and discharging curve figure of lithium titanate material made from embodiment 3；

Fig. 9 is the cyclic curve figure of lithium titanate material made from embodiment 1.

Specific embodiment

The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Embodiment in the present invention, ordinary skill Personnel's all other embodiment obtained under the premise of not doing creative work, shall fall within the protection scope of the present invention.

With embodiment, the present invention is described in detail with reference to the accompanying drawing.