JP2019040685A - Method for manufacturing trilithium phosphate for nonaqueous secondary battery - Google Patents
Method for manufacturing trilithium phosphate for nonaqueous secondary battery Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title abstract description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 60
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000047 product Substances 0.000 claims abstract description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- MJIJRASHNGNNQI-UHFFFAOYSA-K tricalcium lithium phosphate Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Ca+2].[Ca+2].[Ca+2] MJIJRASHNGNNQI-UHFFFAOYSA-K 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 14
- 238000010298 pulverizing process Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 4
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 52
- 239000002245 particle Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 19
- 239000002003 electrode paste Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、非水系二次電池に使用されるリン酸三リチウムの製造方法に関する。 The present invention relates to a method for producing trilithium phosphate used in a non-aqueous secondary battery.
非水系二次電池では、電池性能の向上等を目的として、電池内に無機リン酸塩を含ませることがある。例えば特許文献１には、正極に、リン酸三リチウム（Ｌｉ３ＰＯ４）を含有させた電池が開示されている。このような電池の正極は、例えば、正極活物質とＬｉ３ＰＯ４と結着剤とを適当な溶媒中で混練してなる正極ペーストを、正極集電体に塗工し乾燥することによって作製される。
In a non-aqueous secondary battery, an inorganic phosphate may be included in the battery for the purpose of improving battery performance. For example,
特許文献１等によれば、Ｌｉ３ＰＯ４は、例えば、（ａ）正極活物質の表面を被覆する；（ｂ）非水電解質の酸化分解（典型的には、該非水電解質に含まれる支持塩の加水分解）を抑制する；（ｃ）フッ素含有支持塩（例えばフッ素含有リチウム塩）の加水分解によって生成されるフッ酸（ＨＦ）を捕捉あるいは消費して、非水電解質の酸性度（ｐＨ）を緩和する；のうち少なくとも１つの作用を奏する。Ｌｉ３ＰＯ４は、かかる作用によって、正極活物質からの金属元素の溶出を抑制し、電池の通常使用時の特性、例えば耐久性を向上する効果を奏する。また、電池の過充電時には、電池温度の上昇を抑制して過充電耐性を向上する効果を奏する。
According to
しかしながら、本発明者らの検討によれば、Ｌｉ３ＰＯ４の性状（例えば比表面積や水分量）が適切でない場合、正極の作製に手間取ったり、上記したようなＬｉ３ＰＯ４の添加の効果を十分に得られずに、電池性能が低下したりすることがあった。例えば、Ｌｉ３ＰＯ４の比表面積が大きすぎる場合やＬｉ３ＰＯ４の水分量が多すぎる場合には、正極作製時に正極ペーストの粘度が増大して、正極ペーストの塗工性や取扱性が低下することがあった。また、例えば、Ｌｉ３ＰＯ４の比表面積が小さすぎる場合には、過充電時に電池温度の上昇を抑制する効果が薄くなることがあった。加えて、市販品のＬｉ３ＰＯ４を適切な性状に調整しようとすると、歩留まりが低下して、生産コストが増大する問題があった。 However, according to the study by the present inventors, when the properties of Li 3 PO 4 (for example, specific surface area and moisture content) are not appropriate, it takes time to produce a positive electrode, and the effect of addition of Li 3 PO 4 as described above. May not be sufficiently obtained, and battery performance may be deteriorated. For example, when the specific surface area of Li 3 PO 4 is too large or the water content of Li 3 PO 4 is too large, the viscosity of the positive electrode paste increases during the production of the positive electrode, and the coatability and handleability of the positive electrode paste are increased. There was a decline. In addition, for example, when the specific surface area of Li 3 PO 4 is too small, the effect of suppressing an increase in battery temperature during overcharging may be diminished. In addition, when trying to adjust commercially available Li 3 PO 4 to an appropriate property, there is a problem in that the yield decreases and the production cost increases.
本発明は、かかる点に鑑みてなされたものであり、その目的は、非水系二次電池への使用に適したリン酸三リチウムの製造方法を提供することにある。 This invention is made | formed in view of this point, The objective is to provide the manufacturing method of a trilithium phosphate suitable for the use to a non-aqueous secondary battery.
本発明により、水酸化リチウムとリン酸水溶液とを、水酸化リチウムとリン酸との質量比率が２０〜２８：１８〜２６となるように混合し、ｐＨが６以上８以下となるまで撹拌して、反応物を得る反応工程；上記反応物を、３００℃まで昇温したときの水分検出量が０．０１質量％以上２．５質量％以下となるまで乾燥して、粉末状の乾燥物を得る乾燥工程；上記乾燥物を粉砕し、選別して、比表面積が０．９ｍ２／ｇ以上２０．３ｍ２／ｇ以下の粉末状のリン酸三リチウムを得る分級工程；を包含する、非水系二次電池用のリン酸三リチウムの製造方法が提供される。
According to the present invention, lithium hydroxide and phosphoric acid aqueous solution are mixed so that the mass ratio of lithium hydroxide and phosphoric acid is 20 to 28:18 to 26, and stirred until the pH is 6 or more and 8 or less. A reaction step for obtaining a reaction product; the above reaction product is dried until the amount of water detected when the temperature is raised to 300 ° C. is 0.01% by mass or more and 2.5% by mass or less; the obtained dry process; pulverizing the above dried product, and screened, classification step having a specific surface area obtained following powdery tricalcium phosphate lithium 0.9
上記の製造方法によれば、比表面積と水分量とが適切に調整されたＬｉ３ＰＯ４を好適に得ることができる。上記の製造方法によって製造されたＬｉ３ＰＯ４は、非水系二次電池に好適に使用することができる。すなわち、非水系二次電池に使用された際に、上述のような不具合の発生が抑制されて、その効果をいかんなく発揮することができる。 According to the above manufacturing method, it is possible to obtain a Li 3 PO 4 that the specific surface area and water content is properly adjusted suitably. The Li 3 manufactured by the method of the PO 4 can be suitably used for a nonaqueous secondary battery. That is, when used in a non-aqueous secondary battery, the occurrence of the above-described problems can be suppressed, and the effects can be fully exhibited.
なお、本明細書において、「水分検出量」とは、カールフィッシャー水分計を用いて水分気化法で測定される水分量をいう。加熱温度３００℃で気化する水分には、Ｌｉ３ＰＯ４の表面に物理的に吸着している付着水のみならず、例えば加熱温度２００℃を超えて気化するようなＬｉ３ＰＯ４の結晶水も含まれる。
また、本明細書において「比表面積」とは、一般的な比表面積測定装置を用い、窒素吸着法で測定された比表面積をＢＥＴ法で解析した、所謂、ＢＥＴ比表面積をいう。
In the present specification, the “moisture detection amount” refers to the amount of moisture measured by a moisture vaporization method using a Karl Fischer moisture meter. The water vaporized at a heating temperature of 300 ° C. includes not only adhering water physically adsorbed on the surface of Li 3 PO 4 but also Li 3 PO 4 crystal water that evaporates at a heating temperature exceeding 200 ° C., for example. Is also included.
Further, in this specification, the “specific surface area” means a so-called BET specific surface area obtained by analyzing a specific surface area measured by a nitrogen adsorption method by a BET method using a general specific surface area measuring device.
以下、ここで開示される製造方法の好適な実施形態を説明する。なお、本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、当該分野における従来技術に基づく当業者の設計事項として把握され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。
なお、本明細書において数値範囲をＡ〜Ｂ（ここでＡ，Ｂは任意の数値）と記載している場合は、Ａ以上Ｂ以下を意味するものである。
Hereinafter, preferred embodiments of the manufacturing method disclosed herein will be described. Note that matters other than matters specifically mentioned in the present specification and necessary for the implementation of the present invention can be grasped as design matters of those skilled in the art based on the prior art in this field. The present invention can be carried out based on the contents disclosed in the present specification and common general technical knowledge in the field.
In addition, in this specification, when the numerical range is described as A-B (A and B are arbitrary numerical values), it means A or more and B or less.
図１は、本実施形態に係るリン酸三リチウム（Ｌｉ３ＰＯ４）の製造方法を示すフローチャートである。図１に示すように、本実施形態に係るリン酸三リチウムの製造方法は、次の３つの工程：（ステップＳ１）反応工程；（ステップＳ２）乾燥工程；（ステップＳ３）分級工程を包含する。以下、各工程について詳細に説明する。 FIG. 1 is a flowchart showing a method for producing trilithium phosphate (Li 3 PO 4 ) according to the present embodiment. As shown in FIG. 1, the method for producing trilithium phosphate according to the present embodiment includes the following three steps: (Step S1) reaction step; (Step S2) drying step; (Step S3) classification step. . Hereinafter, each step will be described in detail.
＜（ステップＳ１）反応工程＞
本工程では、まず、水酸化リチウムとリン酸水溶液とを用意する。
水酸化リチウムは、Ｌｉ３ＰＯ４のリチウムイオン（Ｌｉ＋）源となる原料化合物である。水酸化リチウムとしては、市販のものを特に限定なく用いることができる。水酸化リチウムは、固体状であってもよいし液体状であってもよい。
リン酸は、Ｌｉ３ＰＯ４のリン酸イオン（ＰＯ４ ３−）源となる原料化合物である。リン酸水溶液としては、リン酸の濃度が１０〜５０質量％のものを用いるとよい。５０質量％を超える濃度のリン酸水溶液を使用する場合には、リン酸が上記濃度の範囲になるように、予めイオン水等で希釈することが好ましい。上記濃度のリン酸水溶液を用いることにより、例えばヒータや冷却装置等を使用せずとも、反応液の温度を適切に調整することができ、非水系二次電池への使用に適した性状のＬｉ３ＰＯ４を好適に生成させることができる。
<(Step S1) Reaction Step>
In this step, first, lithium hydroxide and an aqueous phosphoric acid solution are prepared.
Lithium hydroxide is a raw material compound that becomes a lithium ion (Li + ) source of Li 3 PO 4 . A commercially available lithium hydroxide can be used without any particular limitation. Lithium hydroxide may be solid or liquid.
Phosphoric acid is a raw material compound that serves as a phosphate ion (PO 4 3− ) source of Li 3 PO 4 . As the phosphoric acid aqueous solution, one having a phosphoric acid concentration of 10 to 50% by mass may be used. When using a phosphoric acid aqueous solution having a concentration exceeding 50% by mass, it is preferable to dilute in advance with ionized water or the like so that phosphoric acid is within the above-mentioned concentration range. By using the phosphoric acid aqueous solution of the above concentration, the temperature of the reaction solution can be adjusted appropriately without using, for example, a heater or a cooling device, and a property of Li suitable for use in a non-aqueous secondary battery. 3 PO 4 can be suitably generated.
すなわち、本発明者らの知見によれば、リン酸の濃度が低すぎると、後の混合・撹拌工程において反応液の温度が低くなり過ぎ、水酸化リチウムとリン酸との反応速度（Ｌｉ３ＰＯ４の生成速度）が遅くなる。このため、粒径の大きな（言い換えれば、比表面積の小さな）Ｌｉ３ＰＯ４粒子が生成されやすくなる。その結果、非水系二次電池の正極に使用された際に、正極活物質の表面を被覆することが難しくなったり、非水電解質の酸性度（ｐＨ）を緩和する効果が得られにくくなったりする。また、過充電時に電池温度の上昇を抑制する効果も発揮されにくくなる。
一方で、リン酸の濃度が高すぎると、後の混合・撹拌工程において反応液の反応温度が高くなり過ぎ、水酸化リチウムとリン酸との反応（Ｌｉ３ＰＯ４の生成）が短時間で終了する。このため、粒径の小さな（言い換えれば、比表面積の大きな）Ｌｉ３ＰＯ４粒子が生成されやすくなる。その結果、Ｌｉ３ＰＯ４を用いて正極を作製する際に、正極ペーストの粘度が増大して塗工性や取扱性が低下しやすくなる。また、正極の抵抗が増大して、通常使用時の電池特性が低下することもある。
したがって、上記濃度のリン酸水溶液を用いることが好ましい。
That is, according to the knowledge of the present inventors, if the concentration of phosphoric acid is too low, the temperature of the reaction solution becomes too low in the subsequent mixing / stirring step, and the reaction rate (Li 3 ) between lithium hydroxide and phosphoric acid. (PO 4 generation speed) becomes slow. For this reason, Li 3 PO 4 particles having a large particle diameter (in other words, a small specific surface area) are easily generated. As a result, when used for the positive electrode of a non-aqueous secondary battery, it is difficult to coat the surface of the positive electrode active material, or the effect of reducing the acidity (pH) of the non-aqueous electrolyte is difficult to obtain. To do. In addition, the effect of suppressing an increase in battery temperature during overcharging is hardly exhibited.
On the other hand, if the concentration of phosphoric acid is too high, the reaction temperature of the reaction solution becomes too high in the subsequent mixing / stirring step, and the reaction between lithium hydroxide and phosphoric acid (generation of Li 3 PO 4 ) takes a short time. finish. For this reason, Li 3 PO 4 particles having a small particle size (in other words, a large specific surface area) are easily generated. As a result, when producing a positive electrode using Li 3 PO 4 , the viscosity of the positive electrode paste increases, and the coatability and handleability tend to decrease. Further, the resistance of the positive electrode may increase, and the battery characteristics during normal use may deteriorate.
Therefore, it is preferable to use an aqueous phosphoric acid solution having the above concentration.
本工程では、次に、水酸化リチウムとリン酸水溶液とを混合して、反応液を調製する。
本実施形態では、水酸化リチウムとリン酸水溶液とを、水酸化リチウムとリン酸との質量比率が２０〜２８：１８〜２６となるように混合する。上記混合比率の範囲に調整することにより、余剰の水酸化リチウムやリン酸が反応液中に残存したり、不純物が生成されたりすることを抑制して、所望の反応物（Ｌｉ３ＰＯ４）を安定的に得ることができる。このため、品質安定性や生産性を向上することができる。
In this step, next, lithium hydroxide and a phosphoric acid aqueous solution are mixed to prepare a reaction solution.
In this embodiment, lithium hydroxide and phosphoric acid aqueous solution are mixed so that the mass ratio of lithium hydroxide and phosphoric acid is 20 to 28:18 to 26. By adjusting the mixing ratio to the above range, it is possible to suppress surplus lithium hydroxide and phosphoric acid from remaining in the reaction solution and generation of impurities, and thereby desired reactants (Li 3 PO 4 ). Can be obtained stably. For this reason, quality stability and productivity can be improved.
すなわち、本発明者らの知見によれば、水酸化リチウムが上記混合比率よりも過剰であると、余剰の水酸化リチウムが反応液中に残存したり、不純物が生成されやすくなったりして、Ｌｉ３ＰＯ４の純度が低下する。加えて、水酸化リチウムは強アルカリ性を示すため、反応液のｐＨが高くなりやすい。このため、反応液のｐＨが最終的に８以下とならないこともある。加えて、Ｌｉ３ＰＯ４を用いて正極を作製する際に、正極ペーストの粘度が増大して塗工性や取扱性が低下しやすくなる。さらには、非水系二次電池の正極に使用された際に、非水電解質の酸性度（ｐＨ）を緩和する効果が得られにくくなる。
一方で、リン酸が上記混合比率よりも過剰であると、余剰のリン酸が反応液中に残存したり、不純物が生成されやすくなったりして、Ｌｉ３ＰＯ４の純度が低下する。加えて、非水系二次電池の正極に使用された際に、正極の抵抗が増大して、通常使用時の電池特性が低下することもある。
したがって、上記混合比率の範囲に調整することが肝要である。
That is, according to the knowledge of the present inventors, if the lithium hydroxide is in excess of the above mixing ratio, excess lithium hydroxide remains in the reaction solution or impurities are easily generated, The purity of Li 3 PO 4 decreases. In addition, since lithium hydroxide exhibits strong alkalinity, the pH of the reaction solution tends to increase. For this reason, the pH of the reaction solution may not finally be 8 or less. In addition, when producing a positive electrode using Li 3 PO 4 , the viscosity of the positive electrode paste is increased, and the coatability and handleability tend to be lowered. Furthermore, when used for the positive electrode of a non-aqueous secondary battery, it is difficult to obtain an effect of reducing the acidity (pH) of the non-aqueous electrolyte.
On the other hand, if the phosphoric acid is in excess of the above mixing ratio, excess phosphoric acid remains in the reaction solution or impurities are likely to be generated, and the purity of Li 3 PO 4 decreases. In addition, when used for the positive electrode of a non-aqueous secondary battery, the resistance of the positive electrode increases, and the battery characteristics during normal use may deteriorate.
Therefore, it is important to adjust to the range of the mixing ratio.
本工程では、次に、典型的には液温２５℃の環境下において、ｐＨが最終的に６〜８となるまで反応液を撹拌する。
撹拌の手段としては、例えばスターラーが挙げられる。撹拌時間は特に限定されないが、例えば０．２〜３時間とするとよい。これにより、非水系二次電池への使用に適した性状のＬｉ３ＰＯ４を好適に生成させることができる。
以上のようにして、ステップＳ１では、水酸化リチウムとリン酸との反応物（Ｌｉ３ＰＯ４）を得ることができる。
In this step, the reaction solution is then stirred until the pH finally becomes 6 to 8, typically in an environment at a liquid temperature of 25 ° C.
Examples of the stirring means include a stirrer. Although stirring time is not specifically limited, For example, it is good to set it as 0.2 to 3 hours. Thereby, Li 3 PO 4 having properties suitable for use in a non-aqueous secondary battery can be suitably generated.
As described above, in step S1, a reaction product (Li 3 PO 4 ) of lithium hydroxide and phosphoric acid can be obtained.
＜（ステップＳ２）乾燥工程＞
本工程は、典型的には、大まかに水分量を調整する第２−１工程と、第２−１工程に次いで、さらに細かく水分量を調整する第２−２工程と、を包含する。
第２−１工程では、ステップＳ１で得られた反応物を脱水する。これによって、大まかに水分量が調整された仮乾燥物が得られる。
脱水の手段としては、例えば遠心脱水機が挙げられる。脱水する時間は、例えば脱水機の種類等によっても異なり得るが、一例として、タナベウイルテック株式会社製のバスケット型遠心分離機Ｏ−２４を使用する場合には、２〜３０分間とするとよい。脱水が不十分であると、次の第２工程に要する時間が長くなって、作業効率や生産性が低下することがある。脱水が過剰であると、次の第２工程において所望の水分量に調整することが難しくなることがある。
<(Step S2) Drying Step>
This step typically includes a step 2-1 for roughly adjusting the amount of water, and a step 2-2 for adjusting the amount of water more finely after the step 2-1.
In step 2-1, the reaction product obtained in step S1 is dehydrated. As a result, a provisionally dried product whose water content is roughly adjusted is obtained.
Examples of the dehydration means include a centrifugal dehydrator. The time for dehydration may vary depending on, for example, the type of dehydrator, but as an example, when a basket type centrifuge O-24 manufactured by Tanabe Wiltech Co., Ltd. is used, it may be 2 to 30 minutes. If the dehydration is insufficient, the time required for the next second step becomes long, and the work efficiency and productivity may decrease. If the dehydration is excessive, it may be difficult to adjust to a desired amount of water in the next second step.
第２−２工程では、第１工程で得られた仮乾燥物を、３００℃まで昇温したときの水分検出量が０．０１〜２．５質量％となるまで本乾燥する。Ｌｉ３ＰＯ４の添加の効果を、長期にわたってより好適に発揮させる観点からは、３００℃まで昇温したときの水分検出量が、概ね０．０５質量％以上、例えば１質量％以上となるまで本乾燥してもよい。また、正極の抵抗をより良く低減して、電池の入出力特性を向上する観点からは、３００℃まで昇温したときの水分検出量が、概ね２質量％以下となるまで本乾燥してもよい。 In the step 2-2, the temporarily dried product obtained in the first step is subjected to main drying until the amount of moisture detected when the temperature is raised to 300 ° C. becomes 0.01 to 2.5% by mass. From the viewpoint of exerting the effect of addition of Li 3 PO 4 more suitably over a long period of time, until the detected amount of water when the temperature is raised to 300 ° C. is approximately 0.05% by mass or more, for example, 1% by mass or more. You may dry this. In addition, from the viewpoint of improving the input / output characteristics of the battery by further reducing the resistance of the positive electrode, even if this dry is performed until the amount of moisture detected when the temperature is raised to 300 ° C. is approximately 2% by mass or less. Good.
本乾燥の手段としては、例えば加熱乾燥機が挙げられる。加熱乾燥機の一例として、旭科学株式会社製の棚式乾燥機ＣＦ−１００Ｃでは、加熱温度と加熱時間とを調節することにより、水分量の調整された乾燥物を得ることができる。加熱温度は、例えば８０〜１５０℃とするとよい。加熱時間は、例えば５〜５０時間とするとよい。これにより、非水系二次電池への使用に適した量の水分を含んだＬｉ３ＰＯ４を好適に得ることができる。 Examples of the main drying means include a heat dryer. As an example of a heat dryer, a shelf-type dryer CF-100C manufactured by Asahi Kagaku Co., Ltd. can obtain a dried product with a moisture content adjusted by adjusting the heating temperature and the heating time. The heating temperature is preferably 80 to 150 ° C., for example. The heating time is preferably 5 to 50 hours, for example. Thus, the Li 3 PO 4 containing an amount of water suitable for use in the nonaqueous secondary battery can be suitably obtained.
なお、本発明者らの知見によれば、例えば加熱乾燥温度が低すぎたり、脱水時間や加熱乾燥時間が短すぎたりして、３００℃まで昇温したときの水分検出量が２．５質量％を超える場合には、Ｌｉ３ＰＯ４を用いて正極を作製する際に、正極ペーストの粘度が増大して塗工性や取扱性が低下しやすくなる。また、非水系二次電池の正極に使用された際に、正極の抵抗が増大して、通常使用時の電池特性が低下することがある。さらに、過充電時に電池温度の上昇を抑制する効果も発揮されにくくなる。
一方で、例えば加熱乾燥温度が高すぎたり、脱水時間や加熱乾燥時間が長すぎたりして、３００℃まで昇温したときの水分検出量が０．０１質量％未満となる場合には、Ｌｉ３ＰＯ４の結晶水が脱水され過ぎて、Ｌｉ３ＰＯ４の結晶構造の安定性が低下する。そのため、粒径の大きな（言い換えれば、比表面積の小さな）Ｌｉ３ＰＯ４粒子が生成されやすくなる。その結果、非水系二次電池の正極に使用された際に、正極活物質の表面を被覆することが難しくなったり、非水電解質の酸性度（ｐＨ）を緩和する効果が得られにくくなったりする。また、過充電時に電池温度の上昇を抑制する効果も発揮されにくくなる。
したがって、上記以外の脱水手段や乾燥手段を採用する場合には、予備実験によって適切な条件を予め決定しておくことが必要である。
According to the knowledge of the present inventors, for example, the moisture detection amount when the temperature is raised to 300 ° C. when the heating and drying temperature is too low or the dehydration time and the heating and drying time are too short is 2.5 masses. In the case of exceeding%, when producing a positive electrode using Li 3 PO 4 , the viscosity of the positive electrode paste is increased and the coating property and the handling property are liable to be lowered. Moreover, when used for the positive electrode of a non-aqueous secondary battery, the resistance of the positive electrode may increase and the battery characteristics during normal use may deteriorate. Furthermore, the effect of suppressing the rise in battery temperature during overcharging is less likely to be exhibited.
On the other hand, when, for example, the heat drying temperature is too high, the dehydration time or the heat drying time is too long, and the amount of water detected when the temperature is raised to 300 ° C. is less than 0.01% by mass, Li The crystal water of 3 PO 4 is excessively dehydrated, and the stability of the crystal structure of Li 3 PO 4 is lowered. Therefore, Li 3 PO 4 particles having a large particle size (in other words, a small specific surface area) are likely to be generated. As a result, when used for the positive electrode of a non-aqueous secondary battery, it is difficult to coat the surface of the positive electrode active material, or the effect of reducing the acidity (pH) of the non-aqueous electrolyte is difficult to obtain. To do. In addition, the effect of suppressing an increase in battery temperature during overcharging is hardly exhibited.
Therefore, when employing a dehydrating means or a drying means other than those described above, it is necessary to determine appropriate conditions in advance through preliminary experiments.
以上のようにして、ステップＳ２では、加熱温度３００℃までに気化する水分量が０．０１〜２．５質量％に調整された乾燥物（Ｌｉ３ＰＯ４）を得ることができる。 As described above, in step S2, a dried product (Li 3 PO 4 ) in which the amount of water vaporized up to a heating temperature of 300 ° C. is adjusted to 0.01 to 2.5% by mass can be obtained.
＜（ステップＳ３）分級工程＞
本工程は、粉砕工程と選別工程とに大別される。粉砕工程は、大まかに粒子の大きさを調整する第３−１工程と、第３−１工程に次いで、さらに細かく粒子の大きさを調整する第３−２工程とを包含する。選別工程は、第３−２工程で得られた粉砕物の中から、所定の比表面積の粉末を選別する工程（第３−３工程）である。
<(Step S3) Classification Step>
This process is roughly divided into a pulverization process and a selection process. The pulverization step includes a step 3-1 for roughly adjusting the particle size and a step 3-2 for finely adjusting the particle size after the step 3-1. The selection step is a step (step 3-3) of selecting powder having a predetermined specific surface area from the pulverized product obtained in step 3-2.
第３−１工程では、ステップＳ２で得られた乾燥物を粗粉砕する。これによって、大まかに粒子の大きさが調整された粗粉砕物が得られる。
粗粉砕の手段としては、例えば破砕型造粒機が挙げられる。例えば、株式会社昭和化学機械工作所製のパワーミルＰ−３では、付属された回転刃の回転数とスクリーンの目開き（スクリーン径）とを調節することで、粉末状の乾燥物を均質な粒径に粉砕することができる。この実施形態において、乾燥物の投入速度は、例えば０．１〜１．０ｋｇ／１０分とするとよい。また、回転刃の回転数は、例えば２０００〜６０００ｒｐｍに設定するとよい。また、スクリーン径は、例えばΦ０．５〜２．０ｍｍとするとよい。これにより、非水系二次電池への使用に適した比表面積のＬｉ３ＰＯ４を得られやすくなる。
In step 3-1, the dried product obtained in step S2 is roughly pulverized. Thereby, a coarsely pulverized product in which the particle size is roughly adjusted is obtained.
Examples of the coarse pulverization means include a crushing granulator. For example, in the power mill P-3 manufactured by Showa Chemical Machinery Co., Ltd., by adjusting the rotation speed of the attached rotary blade and the opening of the screen (screen diameter), the powdery dried product is made into homogeneous particles. Can be crushed to diameter. In this embodiment, the input rate of the dried product may be, for example, 0.1 to 1.0 kg / 10 minutes. Moreover, the rotation speed of a rotary blade is good to set to 2000-6000 rpm, for example. Further, the screen diameter may be Φ0.5 to 2.0 mm, for example. Thereby, it becomes easy to obtain Li 3 PO 4 having a specific surface area suitable for use in a non-aqueous secondary battery.
なお、本発明者らの知見によれば、例えば、乾燥物の投入速度が遅すぎたり、回転数を高く設定しすぎたり、スクリーン径が小さすぎたりすると、粒径の小さな（言い換えれば、比表面積の大きな）Ｌｉ３ＰＯ４粒子が生成されやすくなる。その結果、Ｌｉ３ＰＯ４を用いて正極を作製する際に、正極ペーストの粘度が増大して塗工性や取扱性が低下しやすくなる。また、正極の抵抗が増大して、通常使用時の電池特性が低下することもある。
一方で、乾燥物の投入速度が早すぎたり、回転数を低く設定しすぎたり、スクリーン径が大きすぎたりすると、粒径の大きな（言い換えれば、比表面積の小さな）Ｌｉ３ＰＯ４粒子が生成されやすくなる。その結果、非水系二次電池の正極に使用された際に、正極活物質の表面を被覆することが難しくなったり、非水電解質の酸性度（ｐＨ）を緩和する効果が得られにくくなったりする。また、過充電時に電池温度の上昇を抑制する効果も発揮されにくくなる。
したがって、上記以外の粗粉砕手段を採用する場合には、予備実験によって適切な条件を予め決定しておくことが必要である。
According to the knowledge of the present inventors, for example, if the input speed of the dried product is too slow, the rotational speed is set too high, or the screen diameter is too small, the particle size is small (in other words, the ratio Li 3 PO 4 particles having a large surface area are likely to be generated. As a result, when producing a positive electrode using Li 3 PO 4 , the viscosity of the positive electrode paste increases, and the coatability and handleability tend to decrease. Further, the resistance of the positive electrode may increase, and the battery characteristics during normal use may deteriorate.
On the other hand, if the charging speed of the dried product is too fast, the rotational speed is set too low, or the screen diameter is too large, Li 3 PO 4 particles having a large particle size (in other words, a small specific surface area) are formed. It becomes easy to be done. As a result, when used for the positive electrode of a non-aqueous secondary battery, it is difficult to coat the surface of the positive electrode active material, or the effect of reducing the acidity (pH) of the non-aqueous electrolyte is difficult to obtain. To do. In addition, the effect of suppressing an increase in battery temperature during overcharging is hardly exhibited.
Therefore, when employing coarse pulverization means other than those described above, it is necessary to determine appropriate conditions in advance through preliminary experiments.
第３−２工程では、第３−１工程で得られた粗粉砕物を微粉砕する。これによって、粒子の大きさにバラツキが少ない微粉砕物が得られる。
微粉砕の手段としては、例えばボールミルが挙げられる。例えば、三庄インダストリー株式会社製の２段式回転架台では、高速回転する粉砕刃と固定刃との衝撃・剪断作用によって、粗粉砕物が旋回気流で分級され、微粉末のみが微粉砕物として分離回収される。そのため、粉末状の粗粉砕物を均質な粒径に粉砕することができる。この実施形態では、例えば１つのポットに粗粉砕物を０．５〜２ｋｇ投入して、運転時間を、例えば３〜１５時間に設定するとよい。
In step 3-2, the coarsely pulverized product obtained in step 3-1 is finely pulverized. As a result, a finely pulverized product with less variation in particle size can be obtained.
Examples of the fine pulverization means include a ball mill. For example, in a two-stage rotary mount manufactured by Sanjo Industry Co., Ltd., coarsely pulverized products are classified by swirling airflow by the impact / shearing action of a high-speed rotating pulverizing blade and a fixed blade, and only fine powder is finely pulverized. Separated and recovered. Therefore, the powdery coarsely pulverized product can be pulverized to a uniform particle size. In this embodiment, for example, 0.5 to 2 kg of coarsely pulverized material may be charged into one pot, and the operation time may be set to 3 to 15 hours, for example.
なお、本発明者らの知見によれば、例えば、粗粉砕物の投入量が少なすぎる状態で運転時間を長めに設定すると、上記第３−１工程と同様に、粒径の小さな（言い換えれば、比表面積の大きな）Ｌｉ３ＰＯ４粒子が生成されやすくなる。一方で、粗粉砕物の投入量が多すぎる状態で運転時間を短めに設定すると、上記第３−１工程と同様に、比表面積の小さな（言い換えれば、粒径の大きな）Ｌｉ３ＰＯ４粒子が生成されやすくなる。
したがって、上記以外の微粉砕手段を採用する場合には、予備実験によって適切な条件を予め決定しておくことが必要である。
In addition, according to the knowledge of the present inventors, for example, when the operation time is set to be long in a state where the amount of the coarsely pulverized product is too small, the particle size is small (in other words, in the same manner as in the above-mentioned step 3-1. Li 3 PO 4 particles having a large specific surface area are likely to be generated. On the other hand, when the operation time is set short with the input amount of the coarsely pulverized product being too large, Li 3 PO 4 particles having a small specific surface area (in other words, a large particle size), as in the case of the above-mentioned Step 3-1. Is more likely to be generated.
Therefore, when employing fine pulverization means other than those described above, it is necessary to determine appropriate conditions in advance through preliminary experiments.
第３−３の工程では、第３−２工程で得られた微粉砕物の中から、比表面積が０．９〜２０．３ｍ２／ｇとなる粒子群（粉末）を選別する。上記（ｃ）の酸捕捉効果をより好適に発揮して、過充電耐性をより良く向上する観点からは、比表面積が概ね１．１ｍ２／ｇ以上、例えば３．５ｍ２／ｇ以上の粒子を選別するようにしてもよい。また、正極の抵抗をより良く低減して、電池の入出力特性を向上する観点からは、比表面積が概ね１４．２ｍ２／ｇ以下、例えば１０．３ｍ２／ｇ以下の粒子を選別するようにしてもよい。 In the step 3-3, a particle group (powder) having a specific surface area of 0.9 to 20.3 m 2 / g is selected from the finely pulverized product obtained in the step 3-2. Particles having a specific surface area of about 1.1 m 2 / g or more, for example, 3.5 m 2 / g or more, from the viewpoint of more suitably exhibiting the acid scavenging effect of (c) and better improving overcharge resistance. May be selected. In addition, from the viewpoint of improving the input / output characteristics of the battery by further reducing the resistance of the positive electrode, particles having a specific surface area of approximately 14.2 m 2 / g or less, for example, 10.3 m 2 / g or less are selected. It may be.
選別の手段としては、例えば、所定の粒径以上の粒子を選択的に除去する「篩い」が挙げられる。篩いの一例として、回転乾式篩いが挙げられる。例えば、フロイント・ターボ株式会社製のターボスクリーナーでは、円筒型のスクリーンの内面でロータブレードを高速回転させることにより、微粉砕物を、所定の粒径以上の粒子群と所定の粒径未満の粒子群とに、連続的に篩い分けることができる。この実施形態では、微粉砕物の投入速度を、例えば１０〜５０ｋｇ／時間とするとよい。これにより、非水系二次電池への使用に適した比表面積のＬｉ３ＰＯ４を得られやすくなる。 Examples of the screening means include “sieving” that selectively removes particles having a predetermined particle diameter or more. An example of the sieve is a rotary dry sieve. For example, in a turbo screener manufactured by Freund Turbo, a finely pulverized product is obtained by rotating a rotor blade at a high speed on the inner surface of a cylindrical screen so that a finely pulverized product is less than a predetermined particle size. It can be continuously sieved into particle groups. In this embodiment, the charging speed of the finely pulverized product may be set to, for example, 10 to 50 kg / hour. Thereby, it becomes easy to obtain Li 3 PO 4 having a specific surface area suitable for use in a non-aqueous secondary battery.
なお、本発明者らの知見によれば、例えば、微粉砕物の投入速度が遅すぎると、粒径の小さな（言い換えれば、比表面積の大きな）Ｌｉ３ＰＯ４の割合が多くなりやすい。その結果、上記第３−１工程、第３−２工程と同様に、Ｌｉ３ＰＯ４を用いて正極を作製する際に、正極ペーストの粘度が増大して塗工性や取扱性が低下しやすくなる。また、正極の抵抗が増大して、通常使用時の電池特性が低下することもある。
一方で、微粉砕物の投入速度が速すぎると、粒径の大きな（言い換えれば、比表面積の小さな）Ｌｉ３ＰＯ４の割合が多くなりやすい。その結果、Ｌｉ３ＰＯ４を用いて正極を作製する際に、正極ペーストの濾過が困難になることがある。また、上記第３−１工程、第３−２工程と同様に、通常使用時の電池特性や過充電時の効果が発揮されにくくなる。
したがって、上記以外の選別手段を採用する場合には、予備実験によって適切な条件を予め決定しておくことが必要である。
According to the knowledge of the present inventors, for example, if the charging speed of the finely pulverized product is too slow, the proportion of Li 3 PO 4 having a small particle size (in other words, a large specific surface area) tends to increase. As a result, similar to the above-described Steps 3-1 and 3-2, when producing a positive electrode using Li 3 PO 4 , the viscosity of the positive electrode paste is increased and coating properties and handling properties are reduced. It becomes easy. Further, the resistance of the positive electrode may increase, and the battery characteristics during normal use may deteriorate.
On the other hand, when the charging speed of the finely pulverized product is too fast, the proportion of Li 3 PO 4 having a large particle size (in other words, having a small specific surface area) tends to increase. As a result, when producing a positive electrode using Li 3 PO 4 , filtration of the positive electrode paste may be difficult. Moreover, the battery characteristic at the time of normal use and the effect at the time of overcharge become difficult to be exhibited similarly to the said 3rd-1 process and the 3rd-2 process.
Therefore, when employing a screening means other than those described above, it is necessary to determine appropriate conditions in advance through preliminary experiments.
以上のように、ここに開示される製造方法によれば、水分量と比表面積とが適切に調整されたＬｉ３ＰＯ４を安定的に製造することができる。具体的には、３００℃まで昇温したときの水分検出量が０．０１〜２．５質量％であり、かつ、比表面積が０．９〜２０．３ｍ２／ｇであるＬｉ３ＰＯ４を好適に得ることができる。このことにより、上記Ｌｉ３ＰＯ４は、非水系二次電池に使用された際に、その効果をいかんなく発揮することができる。 As described above, according to the production method disclosed herein, it is possible to stably produce Li 3 PO 4 in which the water content and the specific surface area are appropriately adjusted. Specifically, the detected amount of water when the temperature is raised to 300 ° C. is 0.01 to 2.5% by mass, and the specific surface area is 0.9 to 20.3 m 2 / g, Li 3 PO 4. Can be suitably obtained. Thereby, when the Li 3 PO 4 is used in a non-aqueous secondary battery, the effect can be exhibited.
詳しくは、本発明者らの先願である特願２０１７−０８６２８４号にも記載される通り、Ｌｉ３ＰＯ４の水分検出量を０．０１質量％以上とすることで、Ｌｉ３ＰＯ４の結晶構造の安定性を向上して、Ｌｉ３ＰＯ４の添加の効果を長期にわたって発揮することができる。また、Ｌｉ３ＰＯ４の水分検出量を２．５質量％以下とすることで、正極の抵抗を低減して、電池抵抗の増大を好適に抑制することができる。 Specifically, as described in Japanese Patent Application No. 2017-086284, which is the prior application of the present inventors, the moisture content of Li 3 PO 4 is set to 0.01% by mass or more, whereby Li 3 PO 4 The stability of the crystal structure can be improved and the effect of the addition of Li 3 PO 4 can be exhibited over a long period of time. In addition, by setting the moisture detection amount of Li 3 PO 4 2.5 wt% or less, by reducing the resistance of the positive electrode, it is possible to suitably suppress the increase in battery resistance.
また、本発明者らの先願である特願２０１６−２４４７０３号にも記載される通り、Ｌｉ３ＰＯ４の比表面積を上記範囲とすることで、例えば電池抵抗の増大を好適に抑制することができるともに、上記（ｃ）の酸捕捉効果を好適に発揮して、過充電耐性を向上することができる。 In addition, as described in Japanese Patent Application No. 2006-244703, which is the prior application of the present inventors, by setting the specific surface area of Li 3 PO 4 in the above range, for example, an increase in battery resistance is suitably suppressed. In addition, the acid capture effect of the above (c) can be suitably exhibited to improve overcharge resistance.
本実施形態の製造方法によって製造されたＬｉ３ＰＯ４は、非水系二次電池の構築に好適に用いることができる。特には、非水系二次電池の正極に好適に使用することができる。 Li 3 PO 4 produced by the production method of the present embodiment can be suitably used for construction of a non-aqueous secondary battery. In particular, it can be suitably used for a positive electrode of a non-aqueous secondary battery.
以上、本発明を詳細に説明したが、上記実施形態および実施例は例示にすぎず、ここに開示される発明には上述の具体例を様々に変形、変更したものが含まれる。 As mentioned above, although this invention was demonstrated in detail, the said embodiment and Example are only illustrations and what changed and modified the above-mentioned specific example is included in the invention disclosed here.
Claims (1)
前記反応物を、３００℃まで昇温したときの水分検出量が０．０１質量％以上２．５質量％以下となるまで乾燥して、粉末状の乾燥物を得る乾燥工程；
前記乾燥物を粉砕し、選別して、比表面積が０．９ｍ２／ｇ以上２０．３ｍ２／ｇ以下の粉末状のリン酸三リチウムを得る分級工程；
を包含する、非水系二次電池用のリン酸三リチウムの製造方法。 Lithium hydroxide and phosphoric acid aqueous solution are mixed so that the mass ratio of lithium hydroxide and phosphoric acid is 20 to 28:18 to 26, and stirred until the pH is 6 or more and 8 or less, and the reaction product A reaction step to obtain
A drying step of drying the reaction product until the amount of water detected when the temperature is raised to 300 ° C. is 0.01% by mass or more and 2.5% by mass or less to obtain a powdery dried product;
Classification step in which the dried product was crushed and screened, specific surface area obtained following powdery tricalcium phosphate lithium 0.9 m 2 / g or more 20.3 m 2 / g;
A method for producing trilithium phosphate for a non-aqueous secondary battery.
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