Have you declare it to php.ini to load it? If no, try find this in php.ini and add php_mysqli.dll
;;;;;;;;;;;;;;;;;;;;;;
; Dynamic Extensions ;
;;;;;;;;;;;;;;;;;;;;;;
; If you wish to have an extension loaded automatically, use the following
; syntax:
;
; extension=modulename.extension
;
; For example, on Windows:
;
; extension=msql.dll
;
; ... or under UNIX:
;
; extension=msql.so
;
; ... or with a path:
;
; extension=/path/to/extension/msql.so
;
; If you only provide the name of the extension, PHP will look for it in its
; default extension directory.
;
; Windows Extensions
; Note that ODBC support is built in, so no dll is needed for it.
; Note that many DLL files are located in the extensions/ (PHP 4) ext/ (PHP 5)
; extension folders as well as the separate PECL DLL download (PHP 5).
; Be sure to appropriately set the extension_dir directive.
extension= php_mysqli.dll
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