CN113169328A

CN113169328A - Coated lithium ion rechargeable battery active materials

Info

Publication number: CN113169328A
Application number: CN201980070904.2A
Authority: CN
Inventors: 刘东强; A·弗兰德; A·戈菲; K·扎西伯; J·L·艾伦; S·A·德普三世; T·R·周
Original assignee: Hydro Quebec; US Department of Army
Current assignee: Hydro Quebec; US Department of Army
Priority date: 2018-08-30
Filing date: 2019-08-29
Publication date: 2021-07-23
Also published as: JP7443340B2; EP3844831A1; KR20210062021A; CA3109525A1; EP3844831A4; JP2022522559A; JP2023181319A; WO2020047228A1

Abstract

The present disclosure provides a coated positive electrode active material particle comprising a material having the general chemical formula a_xM_yE_z(XO₄)_qWherein A is an alkali or alkaline earth metal, M comprises cobalt, E is a non-electrochemically active metal, a boron group element or silicon or any alloy or combination thereof, X is phosphorus or sulfur or a combination thereof, 0<x≤1，y>0，z≥0，q>0 and the relative values of x, y, z and q are such that the general chemical formulaAnd (4) balancing the charges. The coated positive electrode active material particle further includes a coating layer including Al₂O₃、ZriZE、TiO₂、ZnO、B₂O₃、MgO₂、La₂O₂LiF and any combination thereof, or LiM¹PO₄Wherein M is¹Is Fe, Cr, Mn, Ni, V or any alloy or combination thereof.

Description

Coated lithium ion rechargeable battery active materials

Priority declaration

The present application claims priority from U.S. provisional patent application serial No. 62/725,060 entitled "coated lithium ion rechargeable battery active material" filed 2018, 8, 30, in accordance with the provisions of 35u.s.c. 119(e), the contents of which are incorporated herein by reference in their entirety.

Technical Field

The present disclosure relates to a coated positive electrode active material for a lithium-ion rechargeable battery, a method of preparing the same, and a lithium-ion rechargeable battery comprising the same.

Background

Many rechargeable batteries contain an organic liquid electrolyte. Organic liquid electrolytes are capable of operating at various voltages and have other advantages. However, the organic liquid electrolyte reacts with some positive electrode active materials to generate gas in the battery. Gases can cause problems in the battery by destroying the battery structure, often resulting in a decrease in battery capacity as the number of charge/discharge cycles increases (capacity fade) or the battery fails to operate at all.

Disclosure of Invention

The present disclosure provides coated positive electrode active material particles comprising an active material having the general chemical formula a_xM_yE_z(XO₄)_qAnd a crystal structure, wherein A is an alkali metal or an alkaline earth metal, M comprises cobalt (Co), E is located at the same structural position in the crystal structure as A and is a non-electrochemically active metal, a boron group element or silicon (Si) or any alloy or combination thereof, X is phosphorus (P) or sulfur (S) or silicon (Si) or a combination thereof, 0<x≤1，y>0，z≥0，q>0 and the relative values of x, y, z and q are such that the chemical formula is charge balanced. The coated positive electrode active material particle further includes a coating layer including Al₂O₃、ZrO₂、TiO₂、ZnO、B₂O₃、MgO₂、La₂O₂LiF and any combination thereof, or LiM¹PO₄Wherein M is¹Is Fe, Cr, Mn, Ni, V or any alloy or combination thereof.

The above-described coated positive electrode active material particles may also be characterized by one or more of the following additional features, which, unless expressly mutually exclusive, may be used in combination with each other or with the description of any other part of this specification, including the specific examples:

i) a may be lithium (Li);

ii) M further comprises cobalt (Co) in the alloy or in combination with at least one other electrochemically active metal;

iii-a) at least one other electrochemically active metal including iron (Fe), chromium (Cr), manganese (Mn), nickel (Ni), vanadium (V) or titanium (Ti);

iii-b) M may be a combination of Co and Fe;

iii-c) M may be a combination of Co and Cr;

iii-d) M may be a combination of Co, Fe and Cr;

iv) z can be greater than 0;

iv-a) E may be Si;

iv-b) E can be a non-electrochemically active metal;

iv-b-1) the non-electrochemically active metal may be magnesium (Mg), calcium (Ca) or strontium (Sr), or zinc (Zn), scandium (Sc), or lanthanum (La), or any alloy or combination thereof;

iv-c) E can be an element of the boron group;

iv-c-1) the boron group element may be aluminum (Al) or gallium (Ga) or a combination thereof;

v)LiM¹PO₄a carbon layer may be included;

vi) the coated positive electrode active material particles can also include a carbon layer between the active material and the coating.

vi-a) the carbon layer may be integrally formed with the active material;

vii) the coating may comprise 0.1 to 20% by weight and include 0.1 and 20% by weight of the coated particle;

viii) the active material may be an attritor-mixed active material;

the present disclosure provides a first method of coating an active material by: the coating precursor solution is applied to the active material particles, and the active material particles with the coating precursor solution are heated to 300 ℃ to 600 ℃ to form a coating on the active material. The active material may have the general chemical formula Li_xM_yE_z(XO₄)_qAnd a crystal structure, wherein A is an alkali metal or an alkaline earth metal, M comprises cobalt (Co), E is located at the same structural position in the crystal structure as A and is a non-electrochemically active metal, a boron group element or silicon (Si) or any alloy or combination thereof, X is phosphorus (P) or sulfur (S) or silicon (Si) or a combination thereof, 0<x≤1，y>0，z≥0，q>0, and phases of x, y, z and qThe pair value makes the chemical formula charge balance; and, the coating precursor solution contains Al capable of forming₂O₃、ZrO₂、TiO₂、ZnO、B₂O₃、MgO₂、La₂O₂A coating precursor of LiF, or any combination thereof, or LiM¹PO₄Coating precursor particles wherein M¹Is Fe, Cr, Mn, Ni, V or any alloy or combination thereof.

The first method described above may be characterized by one or more of the following additional features, which, unless expressly excluded, may be combined with each other or with the description of any other part of this specification, including the specific examples:

i) applying the coating precursor solution may include: spray drying the coating precursor and the active material particles;

i-a) the spray drying may comprise: mixing the coating precursor solution and the active material particles to form a spray-dried solution; and spray drying the spray dried solution;

ii) applying the coating precursor solution can comprise a hydrothermal process comprising: adding active material particles to the coating precursor solution, maintaining the solution at a hydrothermal coating temperature of 70 ℃ to 90 ℃ (inclusive), and drying the solution;

ii-a) the hydrothermal process may further comprise: the solution is kept at the hydrothermal coating temperature for 10 hours to 30 hours inclusive;

iii) the coating precursor solution may comprise an aqueous solvent;

iv) the coating precursor solution may comprise a non-aqueous solvent;

v) the coating precursor solution may comprise a solvent to solute ratio of 99.9:0.1 to 90:10 solvent and coating precursor solute;

vi) the coating precursor solution may comprise a metal or boron salt;

vi-a) the metal or boron salt may include an organometallic salt;

vii) the heating may be continued for 3 to 5 hours.

The present disclosure also provides a second method of coating an active material, the methodThe method comprises the following steps: the coating precursor particles are mixed with the active material particles to form a raw dry mixture, and the dry mixture is subjected to high speed mixing at 8000 to 15000rpm, inclusive. The active material may have the general chemical formula Li_xM_yE_z(XO₄)_qAnd a crystal structure, wherein A is an alkali metal or an alkaline earth metal, M comprises cobalt (Co), E is located at the same structural position in the crystal structure as A and is a non-electrochemically active metal, a boron group element or silicon (Si) or any alloy or combination thereof, X is phosphorus (P) or sulfur (S) or a combination thereof, 0<x≤1，y>0，z≥0，q>0 and the relative values of x, y, z and q are such that the generic chemical charge balances; and the coating precursor particles comprise LiM¹PO₄Wherein M is¹Is Fe, Cr, Mn, Ni, V or any alloy or combination thereof.

The second method described above may be characterized by one or more of the following additional features, which, unless expressly excluded herein, may be combined with each other or with the description of any other part of this specification, including the specific examples:

i) high speed mixing may be carried out for 5 minutes to 15 minutes inclusive.

Both the first and second methods described above may be characterized by one or more of the following additional features, which, unless expressly excluded, may be combined with each other or with the descriptions of any other part of this specification, including the specific examples:

i) a may be lithium (Li);

ii-a) at least one other electrochemically active metal comprises iron (Fe), chromium (Cr), manganese (Mn), nickel (Ni), vanadium (V) or titanium (Ti);

ii-b) M may be a combination of Co and Fe;

ii-c) M may be a combination of Co and Cr;

ii-d) M may be a combination of Co, Fe and Cr;

iii) z can be 0;

iii-a) E may be Si;

iii-b) E can be a non-electrochemically active metal;

iii-b-1) the non-electrochemically active metal may be magnesium (Mg), calcium (Ca) or strontium (Sr), or zinc (Zn), scandium (Sc), or lanthanum (La), or any alloy or combination thereof;

iii-c) E may be an element of the boron group;

iii-c-1) the boron group element may be aluminum (Al) or gallium (Ga) or a combination thereof;

iii-d) X may be P;

iii-e) X may be S;

iii-f) X can be Si;

iv)LiM¹PO₄a carbon layer may be included;

v) the coated particles may include a carbon layer, which may be between the active material and the coating;

v-a) the carbon layer may be integrally formed with the active material;

vi) the coating may comprise 0.1 to 20 wt% and include 0.1 and 20 wt% of the coated particle;

vii) the method may further comprise an attrition mill mixing process for forming the active material, the attrition mill mixing process comprising: subjecting the active material precursor to attrition mill mixing to form active material precursor particles having an average size and heating a stoichiometric amount of the active material precursor to at least a temperature for at least a duration to form an active material;

vii-a) the active material precursor may include: at least one hydroxide, alkali metal phosphate, non-metal phosphate, metal oxide, acetate, oxalate, or carbonate;

vii-a-1) hydroxides may include LiOH, Co (OH)₂、Al(OH)₃At least one of;

vii-a-2) the alkali metal phosphate may comprise LiH₂PO₄Or Li₂HPO₄At least one of;

vii-a-3) the non-metal phosphate may comprise NH₄H₂PO₄Or (NH)₄)₂HPO₄At least one of;

vii-a-4) the metal oxide may include at least one of: cr (chromium) component₂O₃、CaO、MgO、SrO、Al₂O₃、Ga₂O₃、TiO₂、ZnO、Sc₂O₃、La₂O₃Or ZrO₂；

vii-a-5) acetate may include Si (OOCCH)₃)₄；

vii-a-6) the oxalate may include FeC₂O₄、NiC₂O₄Or CoC₂O₄；

vii-a-7) carbonates may include Li₂CO₃、MnCO₃、CoCO₃Or NiCO₃；

vii-b) attritor mixing may comprise: placing the spheres and the active material precursor in an attrition mill at a set weight to weight ratio;

vii-c) attritor blending may include: placing balls and active substance precursors in a grinder container having a total volume not exceeding 75% of the total volume of the grinder container;

vii-d) attritor mixing may be carried out until a particle size plateau is reached;

vii-e) the attritor mixing may be carried out for a time no more than 10% longer than the duration of the particle size plateau;

vii-f) attritor mixing may be carried out for a sufficient duration to allow the yield to reach a plateau in the yield of active substance;

vii-g) the attritor mixing may be carried out for a time no more than 10% longer than a duration sufficient to allow yield to reach a plateau in yield of active material;

vii-h) attritor mixing may be performed for a sufficient duration to reach a plateau of active substance capacity;

vii-i) the attritor mixing may be carried out for a time no more than 10% longer than a duration sufficient to reach a plateau of active material capacity;

vii-j) attritor mixing may be carried out for a mixing duration of 10 hours to 12 hours inclusive;

vii-k) the active material precursor particles may have an average particle size of 1 μm to 700 μm inclusive.

vii-l) attritor mixing may further comprise: filtering the active material precursor particles to remove particles that exceed a set size;

vii-M) A is Li, M is Co or a Co alloy or combination, and X is P, and the temperature is 600 ℃ to 800 ℃ (inclusive);

vii-n) heating during attritor mixing may be carried out for a heating duration of 6 hours to 24 hours inclusive;

vii-o) the yield of attritor mixing may be at least 95 to 99.9%;

vii-p) the purity of the active material may be 95 to 99.9%.

Any of the above-described methods can be used to prepare any of the above-described coated positive electrode active materials, unless clearly mutually exclusive.

The present disclosure also provides an alkali or alkaline earth metal rechargeable battery comprising: an electrolyte comprising a liquid and an alkali metal salt or an alkaline earth metal salt; a negative electrode comprising a surface in contact with the electrolyte, the negative electrode further comprising a negative electrode active material; a positive electrode comprising a surface in contact with an electrolyte, the positive electrode further comprising any positive electrode active material as described above or elsewhere herein or any positive electrode active material prepared according to the above method or a method described elsewhere herein, an electrically insulating separator between the positive electrode and the negative electrode; and a housing surrounding the electrolyte, the electrodes, and the separator.

The above-described batteries may be characterized by one or more of the following additional features, which, unless expressly excluded from the context, may be used in combination with each other or in combination with the descriptions of any other part of this specification, including the specific examples:

i) the battery may further include a pressure application system that applies pressure to at least a portion of the electrode surface in contact with the electrolyte;

i-a) the pressure applying system may include a seal and a pressure applying structure inside the cell;

i-b) the pressure applying structure may comprise a plate and a clamp or screw;

i-c) the pressure applying structure may comprise a pressure bladder;

i-d) the cell may further comprise a gas migration zone;

i-e) the pressure applying structure may apply pressure to at least 90% of the electrode surface in contact with the electrolyte;

i-f) the pressure applied by the pressure applying structure may vary by no more than 5% between any point of applied pressure;

i-g) the pressure exerted by the pressure exerting structure may be from 50psi to 90 psi;

i-h) the pressure exerted by the pressure exerting structure may be from 70psi to 75 psi;

i-i) the electrolyte may comprise an organic liquid;

i-i-1) the organic liquid may comprise an organic carbonate;

i-i-1-a) organic carbonates include Ethylene Carbonate (EC) with dimethyl carbonate (DMC), Propylene Carbonate (PC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), or any combination thereof;

i-i-2) the electrolyte may comprise a lithium salt;

i-i-2-A) the lithium salt comprises: LiPF₆、LiBF₄Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), and lithium trifluoro (sulfonylimide) (LiTFSI), lithium perchlorate (LiClO4), lithium bis (fluorosulfonyl) imide (LiFSI), or any combination thereof;

i-j) the electrolyte may comprise an ionic liquid;

i-j-1) the ionic liquid may comprise a nitrogen (N) -based ionic liquid;

i-j-1-A) the N-based ionic liquid may comprise an ammonium ionic liquid;

the i-j-1-a-) ammonium ionic liquid may comprise N, N-diethyl-N-methyl-N (2-methoxyethyl) ammonium;

i-j-1-B) the N-based ionic liquid may include an imidazolium ionic liquid;

the i-j-1-B-) imidazolium ionic liquids may comprise: ethylmethylimidazolium (EMIm), methylpropylimidazolium (PMIm), butylmethylimidazolium (BMIm), or 1-ethyl-2, 3-dimethylimidazolium, or any combination thereof;

i-j-1-C) the N-based ionic liquid may include a piperidinium ionic liquid;

the i-j-1-C-) piperidinium ionic liquid may comprise: ethyl methyl piperidinium (EMPip), methyl propyl piperidinium (PMPip), or butyl methyl piperidinium (BMPip), or any combination thereof;

i-j-1-D) the N-based ionic liquid may include a pyrrolidinium ionic liquid;

the i-j-1-D-) pyrrolidinium ionic liquids may comprise: ethyl methyl pyrrolidinium (EMPyr), methyl propyl pyrrolidinium (PMPyr), or butyl methyl pyrrolidinium (BMPyr), or any combination thereof;

i-j-2) the ionic liquid may comprise a phosphorus (P) -based ionic liquid;

i-j-2-A) the P-based ionic liquid may comprise a phosphonium ionic liquid;

the i-j-2-a-) phosphonium ionic liquids may comprise: PR₃R 'phosphonium wherein R is butyl, hexyl, or cyclohexyl and R' is methyl, or (CH)₂)₁₃CH₃Tributyl (methyl) phosphonium tosylate, or any combination thereof;

x-j-3) alkali metal salts may include: LiF₂NO₄S₂、LiCF₂SO₃、LiNSO₂(F₃)₂、LiNSO₂(F₂CF₃)₂、LiC₂F₆NO₄S₂Or any combination thereof;

ii) the negative electrode active material may include: metal, carbon, lithium titanate or sodium titanate or lithium niobate or sodium niobate, or a lithium alloy or a sodium alloy.

Brief description of the drawings

Embodiments of the present disclosure may be further understood by reference to the following drawings, wherein like numerals indicate like features. This patent or application document contains at least one drawing executed in color. Copies of this patent or patent application publication and color drawing(s) will be provided by the government agency upon request, after payment of the necessary fee.

Fig. 1A is a schematic cross-sectional view of a coated lithium ion positive electrode active material particle.

Fig. 1B is a schematic cross-sectional view of a coated lithium-ion positive electrode active material particle having a carbon layer.

FIG. 2 is a diagram of multiply substituted lithium cobalt phosphate (LiCo)_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄) X-ray diffraction (XRD) profile of the positive electrode active material. Typical XRD patterns of the final product with trace impurities were marked with x.

Fig. 3 is a representative energy dispersive X-ray spectroscopy (EDX) analysis of positive electrode active materials containing iron (Fe), silicon (Si), and chromium (Cr), showing trace amounts of Si and Cr aggregates. All figures are on a scale of 10 μm.

Fig. 4 is a representative cross-sectional energy dispersive X-ray spectroscopy (EDX) analysis of a positive electrode active material containing Fe, Cr and Si, showing trace amounts of Cr impurities. The scale bar in the leftmost figure is 10 μm. All other figures are on a scale of 5 μm.

Fig. 5A and 5B are a pair of representative Scanning Electron Microscope (SEM) images of the positive electrode active material particles. The scale bar in FIG. 5A is 20 μm. The scale bar in the image of fig. 5B is 5 μm.

FIG. 6 is a flow diagram of a method of mixing precursors with an attrition mill and heating to form an active material.

Fig. 7 is a schematic partial cross-sectional elevation view of a grinding mill suitable for use in the present disclosure.

Fig. 8 is a graph showing the effect of ball to precursor weight to weight ratio on the capacity of active material formed by an attrition mill mixing precursors during attrition mill mixing.

Fig. 9A is a graph showing particle size distribution after 6 hours of attritor mixing at a ball to precursor weight to weight ratio of 8: 1.

Fig. 9B is a graph showing the particle size distribution of the same precursor mixture as fig. 9A after 12 hours of attritor mixing at a ball to precursor weight to weight ratio of 8: 1.

Fig. 10A is a flow diagram of a coating method for forming coated particles.

Fig. 10B is a flow diagram of an alternative coating method for forming coated particles.

Fig. 11 is a battery including a coated active material according to the present disclosure.

Fig. 12 is a schematic cross-sectional view of a battery of the present disclosure.

Fig. 13 is a schematic view of a bottom portion of a battery of the present disclosure.

Fig. 14 is a schematic side view of a spiral pressure cell of the present disclosure.

Fig. 15 is a schematic side view of an air pressure cell of the present disclosure.

Fig. 16 is a graph showing the cycle stability of batteries containing a coated positive electrode active material according to the present disclosure and a comparative uncoated positive electrode active material.

FIG. 17 is 10 wt% c-LiFePO₄-coated LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Scanning Electron Microscope (SEM) images of the positive electrode active material. Marks LiFePO₄And LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄。

FIG. 18 is LiF coated LiCo at different weight% LiF_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Graph of discharge capacity of (1).

FIG. 19 LiCo after 6 or 12 hour attritor mixing at a ball to precursor weight to weight ratio of 6:1_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Active material XRD profile.

FIG. 20 LiCo after 12 hours attritor mixing at a ball to precursor weight to weight ratio of 8:1_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Active material XRD profile.

FIG. 21 LiCo after 12 hours attritor mixing at a ball to precursor weight to weight ratio of 10:1_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Active material XRD profile.

FIG. 22 LiCo after 12 hours attritor mixing at a 12:1 ball to precursor weight to weight ratio_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Active material XRD profile.

FIG. 23 LiCo after 12 hours attritor mixing at a ball to precursor weight to weight ratio of 14:1_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Active material XRD profile.

Detailed Description

The present disclosure relates to a coated positive electrode active material for a lithium-ion rechargeable battery, a method of preparing the same, and a lithium-ion rechargeable battery comprising the same. The coating reduces exposure of the positive electrode active material to the electrolyte, thereby reducing gas generation in the battery.

Referring now to fig. 1A and 1B, coated particles 2 of a lithium ion rechargeable battery positive electrode active material 4 have a coating 6. In fig. 1B, a carbon layer 8 is present between the active material 4 and the coating 6.

Active material

The active material may have the general formula A_xM_yE_zPO₄And a crystal structure, wherein 0<x≤1，y>0 and z ≧ 0, A is an alkali metal or alkaline earth metal, M is cobalt (Co) alone or in an alloy or in combination with another electrochemically active metal, and when z is>At 0, E is located at the same structural position in the crystal structure as a and is a non-electrochemically active metal, a boron group element (group 13, III), or silicon (Si), or any alloy or combination thereof.

The alkali metal (group 1, group I metal) in the active material may be lithium (Li), sodium (Na), or potassium (K). The alkaline earth metal (group 2, group IIA metal) may be magnesium (Mg) or calcium (Ca). The alkali or alkaline earth metal may be present as a migratable cation or may be capable of forming a migratable cation, for example, lithium ion (Li)⁺) Sodium ion (Na)⁺) Potassium ion (K)⁺) Magnesium ion (Mg)² ⁺) Or calcium ion (Ca)³⁺)。

The electrochemically active material is most typically a transition metal, for example, a group 4-12 (also referred to as group IVB-VIII, IB, and IIB) metal. Particularly useful transition metals include: those which easily exist in a state exceeding one valence. Examples include: iron (Fe), chromium (Cr), manganese (Mn), nickel (Ni), vanadium (V) and titanium (Ti).

The non-electrochemically active metal may affect the electrical or electrochemical properties of the active material. For example, non-electrochemically active metals or boron group elements or silicon (Si) may alter the operating voltage of the active material, or increase the electronic conductivity of the active material particles, or improve the cycle life or coulombic efficiency of an electrochemical cell containing the active material. Suitable non-electrochemically active metals include alkaline earth metals (group 2, group II metals), such as magnesium (Mg), calcium (Ca) or strontium (Sr), or zinc (Zn), scandium (Sc), or lanthanum (La), or any alloys or combinations thereof. Suitable boron group elements include aluminum (Al) or gallium (Ga) and combinations thereof.

The alkali or alkaline earth metal, Co and electrochemically active metal, non-electrochemically active metal or boron group element or Si and phosphate are present in relative amounts such that the total active material compound or mixture of compounds is charge balanced. Exemplary active materials include: LiCo_0.9Fe_0.1PO₄、Li_0.95Co_0.85Fe_0.1Cr_0.05PO₄、Li_0.93Co_0.84Fe_0.1Cr_0.05Si_0.01PO₄And LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄。

The active material compound or mixture of compounds exists predominantly in crystalline form (as opposed to amorphous form), which can be confirmed by XRD. In particular, the active material may have a composition similar to lithium cobalt phosphate (LiCoPO) regardless of the presence of other electrochemically or non-electrochemically active metals or boron group elements or Si₄) The olivine crystal structure of (a). An example of an XRD pattern sufficient to confirm the crystal structure is shown in fig. 2.

Carbon layer 8, if present, can be observed by EDX or SEM. The carbon layer 8 may be integrally formed on at least a portion of the outer surface of the active material 4 particles. For example, portions of the carbon layer that are in contact with the outer surface of the active material 4 particles may be covalently bonded to the active material 4. The carbon layer may be at least 80% elemental carbon (C). The carbon layer 8 may comprise 0.01 wt.% to 10 wt.% (inclusive) of the total coated particles 2.

Typically, the particle size of the active material 4 or the active material 4 with the carbon layer 8 may be 1 μm to 999 μm inclusive, 1 μm to 500 μm inclusive, 1 μm to 100 μm inclusive, 10 μm to 999 μm inclusive, 10 μm to 500 μm inclusive, or 10 μm to 100 μm inclusive.

Coating layer

The coating 6 may comprise an electrochemically inactive material, such as a metal or boron oxide, in particular Al₂O₃、ZrO₂、TiO₂、ZnO、B₂O₃、MgO₂、La₂O₂(ii) a Or a non-oxidizing metal, in particular a metal fluoride, for example LiF; and any combination thereof. The coating 6 may also include an electrochemically active material, for example, a non-cobalt-containing lithium metal phosphate material, specifically LiM¹PO₄Wherein M is¹Is Fe, Cr, Mn, Ni, V or any alloy or combination thereof, e.g. LiFePO₄. The electrochemically active coating material may have a carbon layer similar to carbon layer 8, which may be present on active material 4.

The relative amount of coating 6 relative to the total size of the coated particle 2 may vary depending on the coating used. Furthermore, a trade-off is typically made between the specific capacity of the battery comprising the coated particles 2 and the cycle life of the battery. The non-electrochemically active coating 6 often better covers the active material 4 and reduces its reaction with the electrolyte, improving cycle life, but the coating contributes non-electrochemically active weight to the particles, reducing the specific capacity of the battery. Depending on the voltage range, the electrochemically active coating 6 may also participate in the electrochemical reaction, increasing the specific capacity of the battery comprising the coated particles 2, resulting in better performance, such as high rate characteristics of the battery. The electrochemically active coating can reduce side reactions between the active material and the electrolyte and further improve cycle life.

Typically, the coating 6 can comprise 0.1 to 20% (inclusive), 0.1 to 10% (inclusive), 0.1 to 5% (inclusive), 0.5 to 20% (inclusive), 0.5 to 10% (inclusive), 0.5 to 5% (inclusive) of the coated particle 2; 1 wt% to 20 wt% (inclusive), 1 wt% to 10 wt% (inclusive), or 1 wt% to 5 wt% (inclusive).

Method of making coated active materials

While any of the active materials 4 described above may be coated, active materials 4 produced using attritor blending may be particularly useful. Attrition mill mixing can be used to produce commercial levels of active materials with little or no impurities.

The purity of the active material produced using the attritor mixing process, as measured by XRD refinement, can be at least 95%, at least 98%, at least 99%, or between any combination of these values (inclusive), examples of which are provided in fig. 2. The impurities are typically in the form of unreacted precursors or precursors that have reacted to form compounds other than the active material, and a given crystalline impurity compound having a crystalline impurity content of 1% or more can be detected using XRD. Amorphous impurities and impurities with less than 1% content can be detected using EDX, examples of which are provided in fig. 3 and 4.

The active material formed by the attritor mixing exhibits a stable capacity when used in an electrochemical cell, a capacity fade at C/2 of greater than 110 cycles of 50% or less, 40% or less, 20% or less, 10% or less, 5% or less, 1% or less, or a range between (and including) any combination of these values, as compared to the capacity at the tenth cycle at C/2.

The active material 4 formed by the attritor mixing herein may be in particulate form, excluding agglomerated particle batches (averaging no more than 1nm, 10nm, 50nm, 100nm, 500nm, or 999nm, or any range between any combination of these values, inclusive.the particles are referred to as nanoparticles.

The active material particles may form agglomerates, in which case any agglomerates are not included in the above average particle size. However, the agglomerates themselves may be nanoparticles or microparticles. For example, the agglomerates may be particles composed of the active material.

Particle and agglomerate sizes may be evaluated using a Scanning Electron Microscope (SEM), an example of which is shown in fig. 5A and 5B.

Suitable precursors for making the active material will depend on the particular active material to be produced. Typically, the precursor is in solid form, as the process described herein is a solid state manufacturing process. The wet precursors or those obtained as hydrates or containing significant amounts of moisture may be dried prior to use in the disclosed processes. Common precursors include: metal hydroxides, e.g. LiOH, Co (OH)₂And Al (OH)₃(ii) a Alkali metal phosphates, e.g. LiH₂PO₄Or Li₂HPO₄(ii) a An alkaline earth metal phosphate; non-metal phosphates, e.g. NH₄H₂PO₄、(NH₄)₂HPO₄(ii) a Metal oxides, e.g. Cr₂O₃、CaO、MgO、SrO、Al₂O₃、Ga₂O₃、TiO₂、ZnO、Sc₂O₃、La₂O₃Or ZrO₂(ii) a Acetates, e.g. Si (OOCCH)₃)₄(ii) a And oxalates, e.g. FeC₂O₄、NiC₂O₄Or CoC₂O₄(which is typically stored as a hydrate and dried prior to use in the process of the invention); or carbonates, e.g. Li₂CO₃、MnCO₃、CoCO₃Or NiCO₃。

For active materials having a carbon layer 8, carbon layer precursors may also be included in the attritor mixing process described herein. Suitable carbon layer precursors include elemental carbon or carbonaceous materials that decompose to form a carbon coating, e.g., polymers.

Active materials, including those described above, can be made from precursors, including those described above, using a solid-state attritor mixing process, which typically includes attritor mixing at least the non-coating precursor, and then heating the mixture.

An attrition mill mixing process used alone or in combination with a coating process may be used to form at least 1kg, at least 2kg, at least 3kg, at least 5kg, at least 10kg, at least 25kg, at least 50kg, at least 100kg of active material, or an amount thereof in an amount between any two of these listed amounts (inclusive) per batch (e.g., 1kg to 2kg (inclusive), 1kg to 3kg (inclusive), 1kg to 5kg (inclusive), 1kg to 10kg (inclusive), 1kg to 50kg (inclusive), 1kg to 100kg (inclusive), 25kg to 50 kg).

The yield of the attritor mixing process prior to particle size filtration may be at least 80%, at least 85%, or at least 90%, at least 95%, or at least 99%, at least 99.9%, or in an amount between any two of these listed amounts, inclusive, per batch. Yields were measured prior to particle size filtration to exclude direct effects on the selected particle size, rather than to exclude effects on the active particle formation reactions and processes.

For active materials having a carbon layer 8, a carbon layer precursor may be added before the attritor mixes, after the attritor mixes but before heating or after heating, depending largely on the carbon layer to be formed. The carbon layer precursor is typically added prior to mixing in the grinder. One of ordinary skill in the art, using the teachings of this disclosure, and optionally by performing a series of simple experiments in which different carbon layer precursors are added in optional relative amounts at different stages of the process, will be able to readily determine how to incorporate the carbon layer forming step into the methods disclosed herein.

Referring now to fig. 6, the present disclosure provides an attritor mixing process 110 for making active materials. In step 120, the wet precursor or hydrate precursor is dried. In step 130, the precursor, which is too large to be placed in the grinder chamber or ground by the grinder, is cut to a sufficiently small size.

Steps

120 and 130 may be performed in any order.

In step 140, a stoichiometric amount of precursor to be mill mixed is placed in the chamber of the mill and mill mixing is performed to form precursor particles. While generally all of the active material precursors will be subjected to attritor mixing, some of the precursors may be added after attritor mixing.

The mill used in step 140 may be any suitable mill. The grinding mill may be a mixing apparatus having a container, an arm extending from outside the container through a container lid to inside the container, and at least one (and typically a plurality of) paddles coupled to the arm inside the container such that when the arm rotates in response to rotational force applied to the outside of the container, the paddles rotate within the container. If the material is in the vessel it will be affected by the blade and its size will be reduced by a combination of impact and friction with the blade or other material in the vessel.

An exemplary grinder 200 for use in the methods of the present disclosure is shown in fig. 7. The grinder 200 includes a container 210 having a lid 220. The grinding mill 200 further includes a coupling 230 that is attached to an external source of rotational force, such as an electric motor. Coupling 230 is located at a first end of arm 240, which is located outside of container 210. Arm 240 passes through a guide 250 mounted on lid 220 and through lid 220 into the interior of container 210. At least one paddle 260, and typically a plurality of paddles 260 as shown, are located inside vessel 210 and are also coupled to a portion of arm 240 inside vessel 210.

The grinder 200 also includes a plurality of balls 270 (only two balls are shown for clarity).

The balls are also impacted by the paddles and/or material during operation of the mill and help to reduce the size of the precursor.

The spheres used in step 140 may be any size suitable to reduce the precursor to a set particle size within a set time. A 19mm diameter ball may work very well, while a 12.7mm diameter ball may also be suitable.

The spheres may be made of any material that does not react with the precursor to the extent that the yield is reduced to less than 80% or impurities are produced in an amount exceeding 5% of the total impurities. Suitable materials for the ball include: steel, zirconium, or tungsten. The interior of the ball may be made of a different material with an outer coating of a suitable material.

Although these balls help to reduce the size of the precursor, they also occupy the volume in the grinding mill chamber that might otherwise be occupied by the precursor. Thus, the ratio of spheres to total precursor (weight: weight) may be limited to a minimum ratio that still allows for having an active material with a selected particle size or other set properties to be obtained from the overall process 110. For example, fig. 8 shows a comparison of capacity and ball to total precursor (weight: weight), e.g., as may be used for ratio selection.

The particle size of the milled precursor is typically 10 μm or less, 50 μm or less, 100 μm or less, 500 μm or less, 600 μm or less, or 750 μm or less, inclusive, and within any range (inclusive) between any combination of these to (e.g., 1 μm to 10 μm (inclusive), 1 μm to 50 μm (inclusive), 10 μm to 50 μm (inclusive), 1 μm to 600 μm (inclusive)). Suitable weight to weight ratios may vary depending on the precursor used, the precursor size prior to mixing by the attritor, the ball size, and the attritor used, but using the teachings of the present disclosure, one of ordinary skill in the art can readily determine suitable ball to precursor ratios by simply varying these parameters until an acceptable precursor particle size or other set property (e.g., capacity) is obtained.

The total volume of the balls and the precursor in the mill should not exceed the volume specified by the mill manufacturer. Typically, the total volume of the balls and precursor does not exceed 75% of the total volume of the grinder container, leaving sufficient space for the balls and precursor to move during mixing.

For any given set of precursor (at the selected mill premix size), ball: precursor ratio, ball size and mill, the average precursor particle size decreases over time during mill mixing until a particle size plateau is reached. Once the particle size plateau is reached, any additional duration of mill mixing will not further reduce the average precursor particle size by more than 10% compared to the average precursor particle size for the duration at which the particle size plateau was reached. The stationary phase (pateau) can also be readily determined by one of ordinary skill in the art using the teachings of the present disclosure. Although the attritor mixing in step 140 may continue after the particle size plateau is reached, typically step 140 will only continue until the particle size plateau is reached, no more than 10% longer than the duration of the particle size plateau, or for a duration in between (inclusive). Common mixing times to reach plateau include 10-12 hours. Exemplary particle size distributions based on mixing duration that can be used to determine when a plateau is reached are provided in fig. 9A and 9B.

Properties determined at least in part by particle size (e.g., yield or active material capacity) may also exhibit a plateau relative to the attritor mixing duration, and the attritor mixing duration may be set based on the alternative plateau such that the attritor mixing duration only until the plateau is reached is no more than 10% longer than the duration of the particle size plateau, or a duration in between (inclusive).

In some methods, it may be used to control the temperature within the mill during mixing of the mill. For example, some precursors may be temperature sensitive, or it may be used to limit the reaction of the precursor with the active material during mixing by the grinder. If useful, the grinder may further include a cooling system, for example, an external cooling system or a cooling system located within the container, lid, arm, paddle, or any combination thereof. During step 140, the cooling system may maintain the temperature below the set temperature. Alternatively or additionally, the precursor may be cooled prior to the attritor mixing in step 140. Also, or in addition, the attritor may include a thermometer to allow for easy determination during step 140 whether the precursor exceeds a set temperature, in which case it may be discarded or subjected to a quality control process.

After the mill mixing in step 140, a stoichiometric amount of any precursor that has not been subjected to mill mixing is added to the mill mixed precursor particles.

Next, in step 150, the attritor-mixed precursor particles are filtered to exclude particles larger than a set size (typically 10 μm, 50 μm, or 100 μm).

The filtered precursor is then heated in step 160 for a duration to chemically react and form an active material. The temperature to which the precursor is heated may vary depending on the precursor and the active material. The heating in step 50 may be a simple heating process in which the precursor is heated to a set temperature and held at that temperature for a duration of time. The heating in step 160 may also be a more complex, step-wise process, wherein the precursor is heated one or more times to one or more temperatures. The rate at which heating occurs in step 160 may also be controlled to occur at a particular level per minute, and step 160 may even include cooling and then heating throughout the heating process.

For active materials comprising lithium, cobalt and phosphate, the maximum temperature in the heating step 50 may be at least 600 ℃, particularly 600 ℃ to 800 ℃ (inclusive), and may be achieved by a temperature increase of 1 ℃/minute to 10 ℃/minute (inclusive). The heating step may last for at least 6 hours, at least 8 hours, at least 10 hours, or at least 12 hours, at least 18 hours, at least 24 hours, and combinations between these values inclusive, particularly 6 hours to 12 hours inclusive. The heating may be carried out under a reducing atmosphere or an inert atmosphere, for example under nitrogen (N)₂) The reaction is carried out under an atmosphere. Prior to heating, the purge can be at ambient temperature (25 ℃) for 1-4 hours (typically, 3 hours) under a reducing atmosphere or an inert atmosphere (e.g., nitrogen atmosphere).

After heating, the material is cooled in step 170. The cooling may be a simple passive cooling process, an active cooling process, or a step-wise process. The material may be maintained at a particular temperature for a duration of time. The rate at which cooling is performed may also be controlled to occur at a particular level per minute, and step 170 may even include heating and then cooling throughout the cooling process.

The active material is present at the end of the cooling process 170. Depending on the precursor and active material, the active material may even often be present at the end of the heating in step 160. In some methods 110, the heating process 160 and the cooling process 170 may overlap to form one continuous heating/cooling process.

Finally, in step 180, the active material is filtered to exclude particles larger than a set size. For example, 25 μm, 35 μm, 38 μm, 40 μm, 50 μm, or 100 μm.

It should be understood that the attritor mixing process may be performed only in steps 140 and 160 (or step 160/170 instead of step 160 if the heating and cooling form a continuous heating/cooling process). Each of the other steps described in connection with method 110 may be independently omitted.

All or a portion of the steps of method 110 may be performed with limited humidity. For example, all or part of the steps of the method 110 may be performed in a dry room or in a non-aqueous atmosphere (e.g., an inert atmosphere, a hydrogen atmosphere, or a nitrogen atmosphere) (although for most active materials, no such degree of precaution is required) or at an ambient humidity of less than 25% or less than 10%.

Any active material 4 (whether formed by the attritor mixing process 110 or any other process) may have a coating 6 applied using a wet coating process 190A as shown in fig. 10A. In coating process 190a, a coating precursor solution is formed in step 191. The solvent may be an aqueous solution or a non-aqueous solution. For example, an alcohol (e.g., ethanol) may be used as the solvent. The solvent to solute ratio can vary from 99.9:0.1 to 90: 10.

The coating precursor may comprise particles of coating material smaller than the particles of active material 4. For example, the coating precursor may include LiFePO having a carbon layer₄Particles (c-LiFePO)₄). If the maximum average size of the coating precursor particles is not more than 0.8% or 1% of the maximum average size of the active material 4 particles or the particles of active material 4 with the coating 8.

The coating precursor may also comprise a compound that forms the coating 6 upon heating. For example, the coating precursor may be a metal or boron salt that will form part of the coating 6. For example, the coating precursor may beOrganic salts, e.g. C₉H₂₁O₃Al; or inorganic salts, e.g. if the coating 6 is to comprise Al₂O₃Then is Al (NO)₃)₃. If an organic mixture precursor is used, the carbon and hydrogen components will be burned off in a subsequent heating step.

In step 192, the coating precursor solution is applied to the particles of active material 4 or the particles of active material 4 having the coating 8.

The precursor may be applied by spray drying the metal, wherein particles of the active material are added to the coating precursor solution to form a spray dried solution. The spray-dried solution may be mixed prior to spray-drying, for example at a temperature of from 50 ℃ to 70 ℃ (inclusive) or from 55 ℃ to 65 ℃ (inclusive). Mixing may be carried out for 2 hours to 6 hours inclusive or 3 hours to 4 hours inclusive. The spray-dried solution may be stirred while mixing. After mixing the spray-dried solution, the aqueous solution may be spray-dried at a temperature of 90 ℃ to 110 ℃ (inclusive), or at least 100 ℃, and the non-aqueous solution may be spray-dried at another temperature based on the solvent evaporation temperature. The spray drying may be carried out under nitrogen (N)₂) The reaction is carried out under an atmosphere.

Alternatively, in a hydrothermal process, the particles may simply be added to the precursor solution to form a hydrothermal coating solution, which may be maintained at the hydrothermal coating temperature prior to heating. The hydrothermal coating temperature may be 70 ℃ to 90 ℃ (inclusive) or 75 ℃ to 85 ℃ (inclusive). The hydrothermal coating solution may be held at the hydrothermal coating temperature for 10 to 30 hours inclusive, 15 to 25 hours inclusive, or 18 to 22 hours inclusive. The hydrothermal coating solution may be stirred for this entire time or a portion of the time. The hydrothermal coating may already be subsequently dried and the precipitate heated, or drying may take place during heating.

In step 193, the particle with the coating precursor is heated to 300 ℃ to 600 ℃ (inclusive), 300 ℃ to 500 ℃ (inclusive), 300 ℃ to 450 ℃ (inclusive), 350 ℃ to 600 ℃ (inclusive), 350 ℃ to 500 ℃ (inclusive), 350 ℃ to 450 ℃ (inclusive), 400 ℃ to 600 ℃ (inclusive), 400 ℃ to 450 ℃ (inclusive), and the like500 ℃ (inclusive), or 400 ℃ to 450 ℃ (inclusive), especially 400 ℃. The heating is continued for 3 to 5 hours inclusive, in particular for 4 hours. This process is generally insensitive to the rate of temperature rise during heating, but this rate can typically be from 1 deg.C/minute to 10 deg.C/minute. The heating may be carried out under a reducing atmosphere or an inert atmosphere, for example under nitrogen (N)₂) The reaction is carried out under an atmosphere. During heating, the coating 6 is formed to produce the coated particles 2.

In step 194, the coated particles 2 are cooled, typically by passive cooling.

Any active material 4 (whether formed by the attritor mixing process 110 or any other process) may have a coating 6 applied using a dry coating process 190a as shown in fig. 10B. In method 190b, the coating precursor includes particles of coating material that are smaller than the particles of active material 4. For example, the coating precursor may include LiFePO having a carbon layer₄Particles (c-LiFePO)₄). If the maximum average size of the coating precursor particles is not more than 0.8% or 1% of the maximum average size of the active material 4 particles or the particles of active material 4 with the coating 8.

In method 190b, in step 195, the dried particles of active material and the coating precursor are mixed to form a raw mixture. In step 196, the untreated mixture is mixed at high speed to produce coated particles 2. High speed mixing is typically between 8,000rpm and 15,000rpm inclusive, or 8,000rpm and 10,000rpm inclusive, e.g., 8,000rpm, 9,000rpm, or 10,000 rpm. Typical mixing times are 5 minutes to 15 minutes inclusive, 8 minutes to 12 minutes inclusive, 9 minutes to 11 minutes inclusive, or 10 minutes.

All or some of the steps of the

methods

190a and 190b may be performed under conditions that limit humidity. For example, all or part of the steps of the

methods

190a and 190b may be performed in a dry room or in a non-aqueous atmosphere (e.g., an inert atmosphere, a hydrogen atmosphere, or a nitrogen atmosphere) (although for most active materials, no such degree of precaution is required) or at an ambient humidity of less than 25% or less than 10%.

Battery comprising coated active material

The coated active material produced using the above method may be used in a positive electrode of a battery, such as the battery shown in fig. 11. The cell 50 includes a negative electrode (anode) 55, a positive electrode (cathode) 60, and an organic electrolyte 65, and a porous, electrically insulating separator (located in the electrolyte 65) that allows ionic conductivity, but no electronic conductivity, in the organic liquid electrolyte disposed between the negative electrode 55 and the positive electrode 60 within the cell (not shown).

The negative electrode 55 contains an active material. Suitable negative electrode active materials include: lithium metal, carbon (e.g., graphite), lithium titanate or sodium titanate or lithium niobate or sodium niobate, or a lithium alloy or sodium alloy. The negative electrode may further include a binder, a conductive additive, and a current collector.

The positive electrode 60 includes a coated active material as disclosed herein. The positive electrode may further include a thermal and fluorinated carbonate, a sulfolane-based organic solvent, a binder, a conductive additive, and a current collector.

Electrolyte 65 may include an organic liquid, for example, a carbonate, particularly various organic carbonates, specifically Ethylene Carbonate (EC) with dimethyl carbonate (DMC), Propylene Carbonate (PC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), or any combination thereof. Electrolyte 65 may include a lithium salt suitable for previous use with organic liquids, e.g., LiPF₆、LiBF₄Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), and lithium trifluoro (sulfonylimide) (LiTFSI), lithium perchlorate (LiClO4), lithium bis (fluorosulfonyl) imide (LiFSI), or any combination thereof.

Suitable ionic liquids include cationic components, which may include nitrogen (N) -based ionic liquids. N-based ionic liquids include ammonium ionic liquids, such as N, N-diethyl-N-methyl-N (2-methoxyethyl) ammonium. The N-based ionic liquid includes imidazolium ionic liquids, for example, ethylmethylimidazolium (EMIm), methylpropylimidazolium (PMIm), butylmethylimidazolium (BMIm), and 1-ethyl-2, 3-dimethylimidazolium. N-based ionic liquids also include piperidinium ionic liquids, such as ethylmethylpiperidinium (EMPip), methylpropylpiperidinium (PMPep), and butylmethylpiperidinium (BMPip). N-based ionic liquids additionally include pyrrolidinium ionic liquids, e.g., ethyl methyl pyrrolidinium (EMPyr), methyl propyl pyrrolidinium (PMPyr), butyl methyl pyrrolidinium (BMPyr).

Suitable cationic components of ionic liquids also include phosphorus (P) -based ionic liquids. P-based ionic liquids include phosphonium ionic liquids, e.g., PR₃R 'phosphonium wherein R is butyl, hexyl, or cyclohexyl and R' is methyl, or (CH)₂)₁₃CH₃Or tributyl (methyl) phosphonium tosylate.

In any of those described above, any of the cationic components of the ionic liquids may be combined in any combination in the battery of the present disclosure.

The ionic liquid may also include an anionic component. In other ionic liquid forms, for example, bis (fluorosulfonyl) imide (FSI) -based ionic liquids include 1-ethyl-3-methylimidazolium-bis (fluorosulfonyl) imide (EMI-FSI) and N-methyl-N-propylpyrrolidinium-bis (fluorosulfonyl) imide (Py13-FSI), bis (trifluoromethane) sulfonimide (TFSI), and (bis (pentafluoroethanesulfonyl) imide) (BETI). The anionic component of the ionic liquid may also include BF₄Or PF₆。

In any of those described above, any of the anionic components of the ionic liquids may be combined in any combination in the battery of the present disclosure.

Suitable lithium salts for use with ionic liquids may include: LiF₂NO₄S₂、LiCF₂SO₃、LiNSO₂(F₃)₂、LiNSO₂(F₂CF₃)₂Or LiC₂F₆NO₄S₂Or any combination thereof. However, many salts increase the viscosity of the ionic liquid, so that the electrolyte effectively loses ion conductivity, and the battery does not function well. The effect may increase with increasing salt concentration. Some salts (e.g. commonly used LiPF)₆) And will not serve merely as an electrolyte in the ionic liquid.

The electrolyte may also include a plurality of co-solvents (co-solvents) in any combination. Suitable co-solvents include: fluorinated carbonates (FEMC), fluorinated ethers (e.g. CF)₃CH₂OCF₂CHF₂) A nitrile (e.g., succinonitrile or adiponitrile), or sulfolane.

The electrolyte may also include a plurality of additives in any combination. Suitable additives include: trimethylsilylpropionic acid (TMSP), Trimethylsilylphosphite (TMSPi), trimethylsilylboronic acid (TMSB), trimethylboroxine (trimethyoloxine), trimethoxyboroxine or propanesultone.

The cell 55 may have a specific structure to help control gas formation or minimize the effect of any gas formed.

The battery 55 may apply pressure to at least a portion of the electrode surface in contact with the electrolyte. The pressure is applied to 100% of the electrode surface in contact with the electrolyte, or at least 90%, at least 95%, or at least 98% of the electrode surface in contact with the electrolyte. The pressure is sufficient to prevent or reduce gas formation in the cell, or to cause the formed gas to migrate to regions of the cell not between the electrode surfaces in contact with the electrolyte.

Specifically, the battery according to the present invention can apply uniform pressure to the surface of the electrode, and the variation between any points where the pressure is applied is not more than 5%. The pressure can be at least 50psi, at least 60psi, at least 70psi, at least 75psi, at least 80psi, at least 90psi, or any range therebetween and inclusive (e.g., including 70psi to 75psi and inclusive).

Referring to fig. 12-15, the alkali or alkaline earth rechargeable 50 described herein can further include a housing 70 sufficient to house and contain the

electrodes

55, 60, an electrolyte 65 and separator, and a contact 75, the contact 75 allowing current to flow between the negative electrode 55 and the positive electrode 60 when connected by an electrically conductive connector.

The alkali or alkaline earth rechargeable battery 50 may also include a pressure application system that applies pressure to at least a portion of the surfaces of the

electrodes

55 and 60 that are in contact with the electrolyte 65. The pressure applying system may include internal seals and pressure applying structures such as plates (typically housing 70), as well as clamps, screws, pressure bladders, or other structures that apply pressure to the plates or the battery housing to maintain pressure within the battery. The pressure application system may maintain pressure in the sealed portion of the cell, which may inhibit gas formation, but does not cause gas migration once the gas is formed. Some cells 50 may include a gas migration area (gas relocation area) to which the pressure application system tends to direct gas once it is formed.

If present, the seal may be formed of any material that does not react with the electrolyte, negative electrode, positive electrode, or other cell components in contact therewith. While some sealing materials may exhibit some minimal reactivity, in a typical battery of a given design, when cycled at C/2, after a set number of cycles (e.g., at least 100 cycles), such as after at least 100 cycles, after at least 200 cycles, after at least 500 cycles, after at least 2000 cycles, after at least 500 cycles, after at least 1000 cycles, or after a range of any combination between these values, inclusive, the material may be considered non-reactive if it is sufficiently low to avoid seal failure.

Additionally, some pressure application systems may apply pressure continuously after assembly. Other pressure applying systems may be adapted to apply pressure at a set time, for example, shortly before and/or during operation of the battery.

Although fig. 12-15 provide some specific pressure application systems, one of ordinary skill in the art may utilize the teachings of the present disclosure to design other pressure application systems. In addition, although fig. 12-15 show a pressure application system used on a single pouch cell (cell), the pressure application system may be used to apply pressure to multiple cells and any type of cell. Further, while fig. 12-15 show the pressure application system used on flat cells, it may be used on curved, bent, or other non-planar cell forms.

In fig. 12-14, the pressure application system includes an annular seal 80 and a screw 85. As shown, this type of pressure application system seals a portion of an alkali or alkaline earth rechargeable battery 50, wherein

electrodes

55 and 60 are in contact with an electrolyte 65. The screw 85 applies pressure to the housing 70 in the form of a rigid plate. The casing 40 transmits pressure to the portion of the cell 50 within the annular seal 80 located in the groove 90 so that there is pressure when the

electrodes

55 and 60 inside the annular seal 80 are in contact with the electrolyte 65.

Many alternatives to this example can be envisaged and used. For example, only a single seal may be used, the seal need not be located in the groove, the seal may have a shape other than a ring, and pressure applicators other than screws may be used.

In fig. 15, the pressure application system includes a bladder 95, the bladder 95 being inflatable to a set pressure that is transmitted to the housing 70. As shown, the pressure application system does not include any seals and will force the gas formed to reach the gas migration zone 100, especially when pressure is just applied to the housing 70. Thus, the pressure agent system is particularly suitable for applying pressure shortly before and/or during use of the battery.

Many alternatives to this example are also contemplated and used. For example, the bladder 95 may be inflated with other fluids, such as other gases or liquids. For example, the fluid in bladder 95 may be selected to provide insulative (insulating) or thermally conductive properties.

Although not shown, other cells 50 of the present disclosure may obtain a constant pressure on

electrodes

55 and 60 in contact with electrolyte 65 simply by pressurizing electrolyte 65 as electrolyte 65 is added to the cell and then sealing case 70 in a manner that maintains the pressure.

Use of a battery

The batteries comprising coated active materials disclosed herein can be used in a number of applications. For example, it may be a battery in a standard battery format, such as a button cell, jelly roll (jelly roll), or in particular a prismatic battery. The batteries disclosed herein may be used in portable consumer electronics products such as laptops (laptops), phones, notebooks, handheld gaming systems, electronic toys, watches, and fitness trackers. The batteries disclosed herein may also be used in medical devices such as defibrillators, cardiac monitors, fetal monitors, and medical carts (medical carts). The batteries disclosed herein may be used in vehicles such as automobiles, light trucks, heavy trucks, vans (vans), motorcycles, motor scooters (bicycles), battery-assisted bicycles, scooters (scooters), boats (boats), and ships (ship), manned aircraft (piloted aircraft), remotely piloted unmanned aircraft (droopy), military land transportation (mile land transport), and wireless remote control cars. The batteries disclosed herein may also be used in grid storage or large-scale energy supply applications, such as large grid storage units or portable energy supply containers. The batteries disclosed herein may be used in tools, such as hand-held power tools.

The batteries disclosed herein may be connected in series or parallel and may be used in conjunction with control or monitoring devices (e.g., voltage, charge, or temperature monitors, fire suppression devices, and computers programmed to control battery usage or trigger alarms or safety measures) if the battery conditions may be unsafe.

Examples

The following examples are provided merely to explain certain principles related to the present invention. It is not intended, and should not be construed, to disclose or cover the entire disclosure of the invention or any embodiments thereof.

Example 1: on LiCo by hydrothermal method_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Coated with 1 wt.% Al₂O₃

0.8093g of C were added under magnetic stirring₉H₂₁O₃Al was dissolved in 158g of ethanol. Then 20g LiCo was added_0.8 ₂Fe_0.0976Cr_0.0488Si_0.00976PO₄And stirred at 60 ℃ for 4 hours. The mixed solution was then transferred to a 400ml quartz autoclave and heated inThe mixture was kept at 80 ℃ for 20 hours with continuous stirring. After drying, the precipitate is in N₂Then, the mixture was heated at 350 ℃ for 12 hours and then cooled naturally. 1% by weight of Al is produced₂O₃A coated positive electrode active material.

The same procedure was repeated without stirring the mixed solution.

Example 2: by spray drying on LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Coated with 1 wt.% Al₂O₃

0.8093g of C were added under magnetic stirring₉H₂₁O₃Al was dissolved in 158g of ethanol. Then 20g LiCo was added_0.8 ₂Fe_0.0976Cr_0.0488Si_0.00976PO₄And stirred at 60 ℃ for 4 hours. Then, the mixed solution is in N₂Spray-drying at 100 ℃ and then drying the mixture in N₂Heating at 350 deg.C for 12 hr and naturally cooling. 1% by weight of Al is produced₂O₃A coated positive electrode material.

Example 3: contrast cycle stability

For comparison, 1 wt.% of positive electrode active material from examples 1 and 2 or uncoated LiCo was used_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄To prepare a button-type half cell. The cycling stability results are shown in figure 16. All coated materials showed improved cycling stability compared to the uncoated material.

Example 4: on LiCo by high speed dry mixing_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Coated with 10% by weight of c-LiFePO4

2.22g c-LiFePO₄Particles (mean diameter 300nm) and 20g of LiCo with a mean diameter of 38 μm_0.82Fe_0.097 ₆Cr_0.0488Si_0.00976PO₄In 50ml of mini NOBILTA^TMDry blending was carried out at 9000rpm for 10 minutes in a dry mill (NOB-130) (Mikrron corporation, Mikrron, Japan)A clock. FIG. 17 is the 10% by weight c-LiFePO obtained₄Coated LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Representative SEM images of (a).

Example 5: under constant stirring, by hydrothermal method on LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Coated with 4 wt% LiF

0.2572g LiF and 6.4311g LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄Mixed in 267ml of deionized water for 1 hour and then transferred to a 400ml quartz autoclave and held at 200 ℃ for 15 hours with constant stirring. After cooling, the precipitate was centrifuged and washed 3 times with 150ml of deionized water, then in 150ml of ethanol and centrifuged. The remaining powder was air-dried at 80 ℃. The same procedure was repeated using different percentages of LiF from 1 to 4 wt%. Fig. 18 shows that the discharge capacity increases with increasing LiF up to 4 wt%. Similar plateaus are expected for other coatings.

Example 6: mill mixed LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄(6:1 ratio)

930g of LiH₂PO₄675g Co (OH)₂160g of FeC₂O₄·2H₂O, 28.5g Cr₂O₃23g of Cr (OOCCH)₃)₃And 76.3g of acetylene black having a size of less than 500 μm were predried overnight under vacuum at 120 ℃ and then placed in an attritor having a container volume of 9.5L, and 11.3kg of steel balls (ball: precursor weight: weight ratio of 6: 1) having a diameter of 19mm were added. The grinder was run at 400rpm for 6-12 hours. The attritor mixed precursor was transferred to an oven and then in N₂Then heated to 700 ℃ for 12 hours and then cooled naturally in an oven. After the heat treatment, about 1.4 kg of the final product was obtained, which was then filtered through a 38 μm sieve. XRD analysis of the resulting material is presented in fig. 19. The XRD data confirmed that even after only 6 hours of mixing, a mixture with LiCoPO was produced₄Of the same constructionAnd (3) a sexual material.

Example 7: mill mixed LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄(8:1 ratio)

723g of LiH₂PO₄525g of Co (OH)₂122g of FeC₂O₄·2H₂O, 22.2g of Cr₂O₃17.9g of Cr (OOCCH)₃)₃And 59.4g of acetylene black having a size of less than 500 μm were first predried overnight at 120 ℃ under vacuum and then placed in an attritor having a container volume of 9.5L and 11.8kg of steel balls having a diameter of 19mm (ball: precursor weight: weight ratio of 8: 1) were added. The grinder was run at 400rpm for 12 hours. The attritor mixed precursor was transferred to an oven and then in N₂Then heated to 700 ℃ for 12 hours and then cooled naturally in an oven. After the heat treatment, about 1.1 kg of the final product was obtained, which was then filtered through a 38 μm sieve. XRD analysis of the resulting material is presented in fig. 20. XRD data confirmed that LiCoPO was produced with₄Active materials of the same structure.

Example 8: mill mixed LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄(10:1 ratio)

578g of LiH₂PO₄420g of Co (OH)₂97.6g of FeC₂O₄·2H₂O, 17.7g Cr₂O₃14.3g of Cr (OOCCH)₃)₃And 47.5g of acetylene black having a size of less than 500 μm were first predried overnight at 120 ℃ under vacuum and then placed in an attritor having a container volume of 9.5L and 11.8kg of steel balls having a diameter of 19mm (ball: precursor weight: weight ratio of 10: 1) were added. The grinder was run at 400rpm for 12 hours. The attritor mixed precursor was transferred to an oven and then in N₂Then heated to 700 ℃ for 12 hours and then cooled naturally in an oven. After the heat treatment, about 0.9 kg of the final product was obtained, which was then filtered through a 38 μm sieve. XRD analysis of the resulting material is presented in fig. 21. XRD data confirmed that LiCoPO was produced with₄Active materials of the same structure.

Example 9: mill mixed LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄(12:1 ratio)

483g of LiH₂PO₄351g of Co (OH)₂81.5g of FeC₂O₄·2H₂O, 14.8g of Cr₂O₃12.0g of Cr (OOCCH)₃)₃And 39.8g of acetylene black having a size of less than 500 μm were first predried overnight at 120 ℃ under vacuum and then placed in an attritor having a container volume of 9.5L and 11.8kg of steel balls (12:1 balls: precursor weight: weight ratio) having a diameter of 19mm were added. The grinder was run at 400rpm for 12 hours. The attritor mixed precursor was transferred to an oven and then in N₂Then heated to 700 ℃ for 12 hours and then cooled naturally in an oven. After the heat treatment, about 0.73 kg of the final product was obtained, which was then filtered through a 38 μm sieve. XRD analysis of the resulting material is presented in fig. 22. XRD data confirmed that LiCoPO was produced with₄Active materials of the same structure.

Example 10: mill mixed LiCo_0.82Fe_0.0976Cr_0.0488Si_0.00976PO₄(14:1 ratio)

413g of LiH₂PO₄301g of Co (OH)₂70g of FeC₂O₄·2H₂O, 12.7g of Cr₂O₃10.3g of Cr (OOCCH)₃)₃And 34g of acetylene black having a size of less than 500 μm were first predried overnight at 120 ℃ under vacuum and then placed in an attritor having a container volume of 9.5L, and 11.8kg of steel balls having a diameter of 19mm (ball: precursor weight: weight ratio of 14: 1) were added. The grinder was run at 400rpm for 12 hours. The attritor mixed precursor was transferred to an oven and then in N₂Then heated to 700 ℃ for 12 hours and then cooled naturally in an oven. After the heat treatment, about 0.62 kg of the final product was obtained, which was then filtered through a 38 μm sieve. XRD analysis of the resulting material is presented in fig. 23. XRD data confirmed that LiCoPO was produced with₄Active materials of the same structure.

The above-disclosed subject matter is to be considered illustrative, and not restrictive, and the appended claims are intended to cover all such modifications, enhancements, and other embodiments, which fall within the true spirit and scope of the present disclosure. Thus, to the maximum extent allowed by law, the scope of the present disclosure is to be determined by the broadest permissible interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing detailed description.

Claims

1. A coated positive electrode active material particle comprising:

an active material having the chemical formula A_xM_yE_z(XO₄)_qAnd a crystal structure, wherein A is an alkali metal or an alkaline earth metal, M comprises cobalt (Co), E is located at the same structural position in the crystal structure as A and is a non-electrochemically active metal, a boron group element or silicon (Si) or any alloy or combination thereof, X is phosphorus (P) or sulfur (S) or a combination thereof, 0<x≤1，y>0，z≥0，q>0 and the relative values of x, y, z and q are such that the generic chemical charge balances; and

a coating comprising Al₂O₃、ZrO₂、TiO₂、ZnO、B₂O₃、MgO₂、La₂O₂LiF and any combination thereof, or LiM¹PO₄Wherein M is¹Is Fe, Cr, Mn, Ni, V or any alloy or combination thereof.

2. The coated positive electrode active material particle of claim 1, wherein a is lithium (Li).

3. The coated positive electrode active material particle of claim 1, wherein M further comprises cobalt (Co) in an alloy or in combination with at least one other electrochemically active metal.

4. The coated positive electrode active material particle of claim 3, wherein the at least one other electrochemically active metal comprises iron (Fe), chromium (Cr), manganese (Mn), nickel (Ni), vanadium (V), or titanium (Ti).

5. The coated positive electrode active material particle of claim 3, wherein M is a combination of Co and Fe.

6. The coated positive electrode active material particle of claim 3, wherein M is a combination of Co and Cr.

7. The coated positive electrode active material particle of claim 3, wherein M is a combination of Co, Fe, and Cr.

8. The coated positive electrode active material particle of claim 1, wherein z > 0.

9. The coated positive electrode active material particle of claim 8 wherein E is Si.

10. The coated positive electrode active material particle of claim 8, wherein E is a non-electrochemically active material.

11. The coated positive electrode active material particle of claim 10, wherein the non-electrochemically active metal is magnesium (Mg), calcium (Ca) or strontium (Sr), or zinc (Zn), scandium (Sc), or lanthanum (La), or any alloy or combination thereof.

12. The coated positive electrode active material particle of claim 8, wherein E is a boron group element.

13. The coated positive electrode active material particle of claim 12, wherein the boron group element is aluminum (Al) or gallium (Ga) or a combination thereof.

14. The coated positive electrode active material particle of claim 1, wherein X is P.

15. The coated positive electrode active material particle of claim 1, wherein X is S.

16. The coated positive electrode active material particle of claim 1 wherein X is Si.

17. The coated positive electrode active material particle of claim 1, wherein LiM¹PO₄Including a carbon layer.

18. The coated positive electrode active material particle of claim 1, further comprising a carbon layer between the active material and the coating.

19. The coated positive electrode active material particle of claim 18, wherein the carbon layer is integrally formed with the active material.

20. The coated positive electrode active material particle of claim 1, wherein the coating comprises 0.1 wt% to 20 wt% and includes 0.1 wt% and 20 wt% of the coated particle.

21. The coated positive electrode active material particle of claim 1, wherein the active material is an attrition mill mixed active material.

22. A method of coating an active material, the method comprising:

applying a coating precursor solution to the particles of active material;

heating the active material particles having the coating precursor solution to 300 to 600 ℃ to form a coating layer on the active material,

wherein the active material has the chemical formula Li_xM_yE_z(XO₄)_qAnd a crystal structure, wherein M comprises cobalt (Co), E is located at the same structural position in the crystal structure as A,and is a non-electrochemically active metal, a boron group element or silicon (Si) or any alloy or combination thereof, X is phosphorus (P) or sulfur (S) or a combination thereof, 0<x≤1，y>0，z≥0，q>0 and the relative values of x, y, z and q are such that the generic chemical charge balances; and, the coating precursor solution contains Al capable of forming₂O₃、ZrO₂、TiO₂、ZnO、B₂O₃、MgO₂、La₂O₂A coating precursor of LiF, or any combination thereof, or LiM¹PO₄Coating precursor particles wherein M¹Is Fe, Cr, Mn, Ni, V or any alloy or combination thereof.

23. The method of claim 22, wherein applying the coating precursor solution comprises: the coating precursor and active material particles are spray dried.

24. The method of claim 23, wherein spray drying comprises:

mixing the coating precursor solution and the active material particles to form a spray-dried solution; and

the spray-dried solution is spray-dried.

25. The method of claim 22, wherein applying the coating precursor solution comprises: a hydrothermal process comprising:

adding active material particles to the coating precursor solution;

maintaining the solution at a hydrothermal coating temperature of 70 ℃ to 90 ℃ and including 70 ℃ and 90 ℃; and

the solution was allowed to dry.

26. The method of claim 25, the method further comprising: the solution is held at the hydrothermal coating temperature for 10 hours to 30 hours and includes 10 hours and 30 hours.

27. The method of claim 22, wherein the coating precursor solution comprises an aqueous solvent.

28. The method of claim 22, wherein the coating precursor solution comprises a non-aqueous solvent.

29. The method of claim 22, wherein the coating precursor solution comprises a solvent to solute ratio of 99.9:0.1 to 90: 10.

30. The method of claim 22, wherein the coating precursor solution comprises a metal or boron salt.

31. The method of claim 30, wherein the metal or boron salt comprises an organic salt.

32. The method of claim 22, wherein heating is for 3 to 5 hours.

33. A method of coating an active material, the method comprising:

mixing coating precursor particles with active material particles to form a raw dry mixture;

subjecting the dry mixture to high speed mixing at 8,000rpm to 15,000rpm and including 8,000rpm and 15,000 rpm; and

wherein the active material has a chemical formula A_xM_yE_z(XO₄)_qAnd a crystal structure, wherein A is an alkali metal or an alkaline earth metal, M comprises cobalt (Co), E is located at the same structural position in the crystal structure as A and is a non-electrochemically active metal, a boron group element or silicon (Si) or any alloy or combination thereof, X is phosphorus (P) or sulfur (S) or a combination thereof, 0<x≤1，y>0，z≥0，q>0 and the relative values of x, y, z and q are such that the generic chemical charge balances; and the coating precursor particles comprise LiM¹PO₄Wherein M is¹Is Fe, Cr, Mn, Ni, V or any alloy or combination thereof.

34. The method of claim 33, wherein the high speed mixing is performed for 5 minutes to 15 minutes and including 5 and 15 minutes.

35. The method of claim 22 or claim 33, wherein M is lithium (Li).

36. A method according to claim 22 or claim 33, wherein M further comprises cobalt (Co) in the alloy or in combination with at least one other electrochemically active metal.

37. The method of claim 36, wherein the at least one other electrochemically active metal comprises iron (Fe), chromium (Cr), manganese (Mn), nickel (Ni), vanadium (V), or titanium (Ti).

38. The method of claim 36, wherein M is a combination of Co and Fe.

39. The method of claim 36, wherein M is a combination of Co and Cr.

40. The method of claim 36, wherein M is a combination of Co, Fe, and Cr.

41. The method of claim 22 or claim 33, wherein z > 0.

42. The method of claim 41, wherein E is Si.

43. The method of claim 41, wherein E is a non-electrochemically active metal.

44. The method of claim 43, wherein the non-electrochemically active metal is magnesium (Mg), calcium (Ca) or strontium (Sr), or zinc (Zn), scandium (Sc), or lanthanum (La), or any alloy or combination thereof.

45. The method of claim 41, wherein E is a boron group element.

46. The method of claim 45, wherein the boron group element is aluminum (Al) or gallium (Ga) or a combination thereof.

47. The method of claim 33, wherein X is P.

48. The method of claim 33, wherein X is S.

49. The method of claim 33, wherein X is Si.

50. The method of claim 22 or claim 33, wherein LiM¹PO₄Including a carbon layer.

51. A method according to claim 22 or claim 33, further comprising a carbon layer between the active material metal and the coating.

52. A method according to claim 51, wherein the carbon layer is integrally formed with the active material.

53. A method according to claim 22 or claim 33, wherein the coating comprises 0.1 to 20 wt% and including 0.1 and 20 wt% of the coated particle.

54. The method of claim 22 or claim 33, further comprising an attrition mill mixing process for forming the active material, the attrition mill mixing process comprising:

subjecting the active material to attrition mill mixing to form active material precursor particles having an average size; and

a stoichiometric amount of an active material precursor is heated to at least a temperature for at least a period of time to form an active material.

55. The method of claim 54, wherein the active material precursor comprises: at least one hydroxide, alkali metal phosphate or alkaline earth metal phosphate, non-metal phosphate, metal oxide, acetate, oxalate, or carbonate.

56. The method of claim 55, wherein the hydroxide comprises LiOH, Co (OH)₂、Al(OH)₃At least one of (1).

57. The method of claim 55, wherein the alkali metal phosphate comprises LiH₂PO₄Or Li₂HPO₄At least one of (1).

58. The method of claim 55, wherein the non-metallic phosphate comprises NH₄H₂PO₄Or (NH)₄)₂HPO₄At least one of (1).

59. The method of claim 55, wherein the metal oxide comprises at least one of: cr (chromium) component₂O₃、CaO、MgO、SrO、Al₂O₃、Ga₂O₃、TiO₂、ZnO、Sc₂O₃、La₂O₃Or ZrO₂。

60. The method of claim 55, wherein acetate comprises Si (OOCCH)₃)₄。

61. The method of claim 55, wherein the oxalate comprises FeC₂O₄、NiC₂O₄Or CoC₂O₄。

62. The method of claim 55, wherein the carbonate comprises Li₂CO₃、MnCO₃、CoCO₃Or NiCO₃。

63. The method of claim 54, wherein the attritor mixing comprises: the spheres and active material precursor were placed in an attritor at a set weight to weight ratio.

64. The method of claim 54, wherein the attritor mixing comprises: placing the spheres and the active material precursor in a grinder container having a total volume that does not exceed 75% of a total volume of the grinder container.

65. A method as claimed in claim 54 wherein attritor mixing is carried out until a particle size plateau is reached.

66. A method as claimed in claim 54, wherein the attritor mixing is carried out for a period of no more than 10% longer than the duration of the particle size plateau.

67. The method of claim 54, wherein the attritor mixing is performed for a duration sufficient to achieve a yield plateau for the yield of active material.

68. The method of claim 54, wherein the attritor mixing is performed for a time no greater than 10% longer than a duration sufficient to allow the yield to reach a plateau in the yield of active material.

69. The method of claim 54, wherein the attritor mixing is performed for a sufficient duration to reach an active material capacity plateau.

70. The method of claim 54, wherein the attritor mixing is performed for a time no more than 10% longer than a duration sufficient to reach a plateau of active material capacity.

71. The method of claim 54, wherein the attritor mixing is performed for 10 hours to 12 hours and includes a mixing duration of 10 hours and 12 hours.

72. The method of claim 54, wherein the active material precursor particles have an average particle size of 1 μm to 700 μm and include 1 μm and 700 μm.

73. The method of claim 72, further comprising: the active material precursor particles are filtered to remove particles that exceed a set size.

74. The method of claim 54, wherein A is Li, M is Co or a Co alloy or combination, and X is P, and the temperature is 600 ℃ to 800 ℃ and includes 600 ℃ and 800 ℃.

75. The method of claim 54, wherein the thermal heating is for a heating duration of 6 hours to 24 hours and including 6 hours and 24 hours.

76. The method of claim 54, wherein the yield of the method is at least 95% to 99.9%.

77. The method of claim 54, wherein the active material has a purity of 95% to 99.9%.

78. An alkali or alkaline earth rechargeable battery comprising:

an electrolyte comprising a liquid and an alkali metal salt or an alkaline earth metal salt;

a negative electrode comprising a surface in contact with the electrolyte, the negative electrode comprising a negative electrode active material;

a positive electrode comprising a surface in contact with an electrolyte, the positive electrode comprising a positive electrode active material as defined in any one of claims 1 to 18 or prepared according to any one of claims 19 to 70;

an electrically insulating separator between the positive electrode and the negative electrode;

a housing surrounding the electrolyte, the electrodes, and the separator.

79. The cell of claim 78 further comprising a pressure application system operable to apply pressure to at least a portion of the electrode surface in contact with the electrolyte.

80. The battery of claim 79, wherein the pressure applying system comprises a seal and a pressure applying structure inside the battery.

81. The battery of claim 79, wherein the pressure applying structure comprises a plate and a clamp or screw.

82. The battery of claim 79, wherein the pressure applying structure comprises a pressure bladder.

83. The cell of claim 79 further comprising a gas migration zone.

84. The battery of claim 79, wherein the pressure applying structure applies pressure to at least 90% of the electrode surface in contact with the electrolyte.

85. The battery of claim 79, wherein the pressure applied by the pressure applying structure does not vary by more than 5% between any points of applied pressure.

86. The battery of claim 79, wherein the pressure applying structure applies a pressure of 50psi to 90 psi.

87. The battery of claim 79, wherein the pressure applying structure applies a pressure of 70psi to 75 psi.

88. The battery of claim 79, wherein the electrolyte comprises an organic liquid.

89. The battery of claim 88, wherein the organic liquid comprises an organic carbonate.

90. The battery of claim 89, wherein the organic carbonate comprises Ethylene Carbonate (EC) with dimethyl carbonate (DMC), Propylene Carbonate (PC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), or any combination thereof.

91. The battery of claim 79, wherein the electrolyte comprises a lithium salt.

92. The battery of claim 91, wherein the lithium salt comprises: LiPF₆、LiBF₄Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), and lithium trifluoro (sulfonylimide) (LiTFSI), lithium perchlorate (LiClO4), lithium bis (fluorosulfonyl) imide (LiFSI), or any combination thereof.

93. The battery of claim 79, wherein the electrolyte comprises an ionic liquid.

94. The battery of claim 93, wherein the ionic liquid comprises a nitrogen (N) -based ionic liquid.

95. The battery of claim 94, wherein the N-based ionic liquid comprises an ammonium ionic liquid.

96. The battery of claim 95, wherein the ammonium ionic liquid comprises N, N-diethyl-N-methyl-N (2-methoxyethyl) ammonium.

97. The battery of claim 94, wherein the N-based ionic liquid comprises an imidazolium ionic liquid.

98. The battery of claim 97, wherein the imidazolium ionic liquid comprises: ethyl methyl imidazolium (EMIm), methyl propyl imidazolium (PMIm), butyl methyl imidazolium (BMIm), or 1-ethyl-2, 3-dimethyl imidazolium, or any combination thereof.

99. The battery of claim 94, wherein the N-based ionic liquid comprises a piperidinium ionic liquid.

100. The battery of claim 99, wherein the piperidinium ionic liquid comprises: ethyl methyl piperidinium (EMPip), methyl propyl piperidinium (PMPip), or butyl methyl piperidinium (BMPip), or any combination thereof.

101. The battery of claim 94, wherein the N-based ionic liquid comprises a pyrrolidinium ionic liquid.

102. The battery of claim 101, wherein the pyrrolidinium ionic liquid comprises: ethyl methyl pyrrolidinium (EMPyr), methyl propyl pyrrolidinium (PMPyr), or butyl methyl pyrrolidinium (BMPyr), or any combination thereof.

103. The battery of claim 93, wherein the ionic liquid comprises a phosphorus (P) -based ionic liquid.

104. The battery of claim 103, wherein the P-based ionic liquid comprises a phosphonium ionic liquid.

105. The battery of claim 104, wherein the phosphonium ionic liquid comprises: PR₃R 'phosphonium wherein R is butyl, hexyl, or cyclohexyl and R' is methyl, or (CH)₂)₁₃CH₃Tributyl (methyl) phosphonium tosylate, or any combination thereof.

106. The battery of claim 93, wherein the alkali metal salt comprises: LiF₂NO₄S₂、LiCF₂SO₃、LiNSO₂(F₃)₂、LiNSO₂(F₂CF₃)₂、LiC₂F₆NO₄S₂Or any combination thereof.

107. The battery of claim 79, wherein the negative electrode active material comprises: metal, carbon, lithium titanate or sodium titanate or lithium niobate or sodium niobate, or a lithium alloy or a sodium alloy.